WO2019230700A1 - 補強繊維及びその製造方法、並びにそれを用いた成形体 - Google Patents
補強繊維及びその製造方法、並びにそれを用いた成形体 Download PDFInfo
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- WO2019230700A1 WO2019230700A1 PCT/JP2019/021036 JP2019021036W WO2019230700A1 WO 2019230700 A1 WO2019230700 A1 WO 2019230700A1 JP 2019021036 W JP2019021036 W JP 2019021036W WO 2019230700 A1 WO2019230700 A1 WO 2019230700A1
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- conjugated diene
- rubber
- diene rubber
- fiber
- reinforcing fiber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/20—Incorporating sulfur atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/22—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J107/00—Adhesives based on natural rubber
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J115/00—Adhesives based on rubber derivatives
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0042—Reinforcements made of synthetic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Definitions
- the present invention relates to a reinforcing fiber excellent in adhesiveness to rubber, a method for producing the same, and a molded body using the same.
- Patent Document 3 proposes a technique using an adhesive including an adhesive compound having an unsaturated carbon bond and an epoxy group that reacts with a vulcanizing agent used for rubber vulcanization.
- Patent Document 4 includes (blocked) isocyanate compound and / or amine curing agent (A), epoxy compound (B), and rubber latex (C), and an organic fiber cord that does not contain resorcinol and formalin.
- a bonding method using an adhesive composition for a liquid has been proposed.
- Patent Document 5 proposes a technique of dividing and reducing the diameter by mechanical shearing force as a rubber reinforcing fiber to which liquid rubber is adhered.
- the method using the adhesive described in Patent Document 3 is greatly inferior to the conventional method using RFL. There is also a description that a blocked isocyanate is added in order to improve the adhesive force. In this case, however, it is necessary to perform a heat treatment at a high temperature and / or for a long time in order to polymerize the blocked isocyanate on the adherend fiber. There was a possibility of deteriorating the adherend fiber.
- the method using the adhesive described in Patent Document 4 has an adhesive force equal to or higher than that of the conventional method using RFL, the adhesive layer is substantially formed after forming the adhesive layer on the surface of the organic fiber cord. Needed to be heat treated at high temperatures (180 ° C. and 240 ° C.).
- Patent Document 5 When organic fibers such as PVA fibers and PET fibers that are often used as reinforcing fibers are treated by such a method, there is a risk that the performance as the reinforcing fibers may deteriorate due to deterioration.
- the technique described in Patent Document 5 is obtained by dividing and reducing the diameter of rubber reinforcing fibers by mechanical shearing force, and has excellent dispersibility without impairing the basic performance of the matrix rubber used in the production of a rubber molded body.
- this is a technique for improving the reinforcement, further improvement in the adhesive strength with rubber has been demanded. Therefore, there has been a demand for a bonding method that does not deteriorate general-purpose fibers while having the same adhesive strength as a conventional method using RFL.
- An object of the present invention has been made in view of the above-described conventional problems, and is a reinforcing fiber using an adhesive component that does not contain resorcin and formalin, and has excellent adhesion to rubber and a method for producing the same And providing a molded body using the same.
- the present inventors have used a modified conjugated diene rubber having a hydrogen bonding functional group as a part of the conjugated diene rubber as an adhesive component, and the modified conjugate.
- the number of hydrogen-bonding functional groups in the diene rubber within a specific range, it was found that a reinforcing fiber excellent in adhesiveness to rubber can be obtained without using resorcinol and formalin, and the present invention was completed. It was.
- the present invention relates to the following [1] to [3].
- the adhesive component includes a modified conjugated diene rubber having a hydrogen bonding functional group in a part of the conjugated diene rubber, and the number of hydrogen bonding functional groups in the modified conjugated diene rubber is an average per molecule.
- 2 to 150 reinforcing fibers [2] The method for producing a reinforcing fiber according to [1].
- [3] A molded body using the reinforcing fiber according to [1].
- the present invention can provide a reinforcing fiber using an adhesive component that does not contain resorcin and formalin, and has excellent adhesion to rubber, a method for producing the same, and a molded body using the same.
- the reinforcing fiber of the present invention is a reinforcing fiber containing a hydrophilic fiber and an adhesive component, and has the adhesive component on at least a part of the surface of the hydrophilic fiber, and the adhesive component is a conjugated diene rubber.
- a modified conjugated diene rubber having a hydrogen bondable functional group in part hereinafter also referred to as “modified conjugated diene rubber”
- modified conjugated diene rubber A modified conjugated diene rubber having a hydrogen bondable functional group in part
- the average is 2 to 150.
- the modified conjugated diene rubber is present on at least a part of the surface of the hydrophilic fiber, the wettability between the reinforcing fiber and the rubber is improved, and the multiple bond of the modified conjugated diene rubber is included. Since the rubber and the like react to form a bond, a reinforcing fiber having an excellent adhesive force can be obtained.
- the adhesive component may be contained in the hydrophilic fiber, but is present on at least a part of the surface of the hydrophilic fiber.
- the adhesive component used in the present invention can provide a reinforcing fiber excellent in adhesiveness to rubber even if it does not contain formaldehyde harmful to the human body and a resin made from formaldehyde as a raw material.
- the adhesive component includes a resin using formaldehyde as a raw material
- examples of the resin include resorcin / formaldehyde resin, phenol / formaldehyde resin, melamine / formaldehyde resin, and derivatives thereof.
- the content thereof is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, with respect to 100 parts by mass of the conjugated diene rubber. 1 part by mass or less is still more preferable, and it is particularly preferable that it is substantially not contained.
- the formaldehyde content can be measured by using HPLC or the like after extracting the adhesive component from the reinforcing fiber with a solvent such as toluene.
- the adhesive component used in the present invention includes a modified conjugated diene rubber having a hydrogen bondable functional group in a part of the conjugated diene rubber, and the number of hydrogen bondable functional groups in the modified conjugated diene rubber per molecule. There is no particular limitation as long as it is 2 to 150 on average. According to the present invention, the modified conjugated diene rubber interacts with each of the rubber and the hydrophilic fiber as the adherend, thereby bonding them together. Since the modified conjugated diene rubber has a molecular structure similar to that of the adherend rubber, at least a part thereof is entangled and interacts.
- the modified conjugated diene rubber and the adherend rubber form a covalent bond by vulcanization, thereby generating a strong cohesive force and improving adhesiveness. Furthermore, it is considered that the adhesiveness is improved by the interaction of the hydrogen bonding functional group contained in the modified conjugated diene rubber with the hydrophilic fiber centering on hydrogen bonding.
- hydrogen bond refers to an electrically positively hydrogen atom (donor) that is bonded to an atom (O, N, S, etc.) having a high electronegativity and has a lone electron pair. It means a binding interaction formed with a negative atom (acceptor).
- the “hydrogen-bonding functional group” is a functional group that can function as a donor and an acceptor in the hydrogen bond. Specifically, hydroxy group, ether group, mercapto group, carboxyl group, carbonyl group, aldehyde group, amino group, imino group, imidazole group, urethane group, amide group, urea group, isocyanate group, nitrile group, silanol group and These derivatives are mentioned. Examples of the aldehyde group derivatives include acetalized derivatives thereof. Examples of the derivative of the carboxyl group include a salt thereof, an esterified product thereof, an amidated product thereof, and an acid anhydride thereof.
- Examples of silanol group derivatives include esterified products thereof.
- Examples of the carboxyl group include a group derived from a monocarboxylic acid and a group derived from a dicarboxylic acid. Among these, one or more selected from a hydroxy group; an aldehyde group and an acetalized product thereof; a carboxyl group, a salt thereof, an esterified product thereof, and an acid anhydride thereof; and a silanol group and an esterified product thereof are preferable.
- the number of hydrogen-bonding functional groups in the modified conjugated diene rubber is 2 to 150 on average per molecule.
- the number of hydrogen-bonding functional groups is 2 or more, preferably 3 or more, more preferably 4 or more on an average per molecule from the viewpoint of obtaining a reinforcing fiber having excellent rubber adhesion.
- the number of the hydrogen bonding functional groups is 150 or less, preferably 120 on average per molecule from the viewpoint of controlling the viscosity of the modified conjugated diene rubber to an appropriate range and improving the handleability.
- the number is more preferably 80 or less, still more preferably 40 or less, still more preferably 30 or less, still more preferably 25 or less, still more preferably 20 or less, and still more preferably 10 or less.
- the average number of hydrogen bonding functional groups per molecule of the modified conjugated diene rubber is calculated based on the following formula from the equivalent (g / eq) of hydrogen bonding functional groups of the modified conjugated diene rubber and the number average molecular weight Mn in terms of styrene. Is done.
- the equivalent of hydrogen-bonding functional groups of the modified conjugated diene rubber means the mass of the conjugated diene bonded to one hydrogen-bonding functional group and other monomers other than the conjugated diene contained if necessary. To do.
- Average number of hydrogen bonding functional groups per molecule [(Number average molecular weight (Mn)) / (Molecular weight of styrene unit) ⁇ (Average of monomer units other than conjugated diene and conjugated diene contained as necessary) Molecular weight)] / (equivalent of hydrogen bonding functional group)
- the calculation method of the equivalent of a hydrogen bondable functional group can be suitably selected according to the kind of hydrogen bondable functional group.
- the modified conjugated diene rubber contains at least a monomer unit derived from a conjugated diene in the molecule (hereinafter also referred to as “conjugated diene unit”), and preferably at least a part of the polymer chain has a conjugated diene. It contains units and has a hydrogen-bonding functional group on the side chain or terminal of the polymer chain.
- conjugated diene monomer examples include butadiene, 2-methyl-1,3-butadiene (hereinafter also referred to as “isoprene”), 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, ⁇ -Farnesene, ⁇ -farnesene, chloroprene and the like. These conjugated dienes may be used alone or in combination of two or more.
- the modified conjugated diene rubber preferably has a monomer unit derived from one or more selected from butadiene and isoprene in the molecule from the viewpoint of reactivity during vulcanization, and is a monomer unit derived from butadiene. It is more preferable to have.
- Examples of a method for obtaining a modified conjugated diene rubber include a method obtained by adding a modifying compound to a polymerized product of a conjugated diene monomer (hereinafter also referred to as “production method (1)”), a conjugated diene monomer Of a polymer and a radically polymerizable compound having a hydrogen bonding functional group (hereinafter also referred to as “production method (2)”), an unmodified conjugated diene monomer having a polymerization active terminal
- production method (3) A method of adding a modifying compound capable of reacting with the polymerization active terminal before adding a polymerization terminator to the polymerized product
- Production method (1) is a method of adding a modified compound to a polymerized product of a conjugated diene monomer, that is, an unmodified conjugated diene rubber (hereinafter also referred to as “unmodified conjugated diene rubber”).
- the unmodified conjugated diene rubber can be obtained by polymerizing a conjugated diene and, if necessary, other monomers other than the conjugated diene by, for example, an emulsion polymerization method or a solution polymerization method.
- emulsion polymerization method a known method or a method according to a known method can be applied.
- a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator.
- the emulsifier include a long chain fatty acid salt having 10 or more carbon atoms and a rosin acid salt.
- the long chain fatty acid salts include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and the like.
- a dispersion solvent water is usually used, and a water-soluble organic solvent such as methanol and ethanol may be contained as long as stability during polymerization is not hindered.
- the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide, and the like.
- a chain transfer agent may be used.
- chain transfer agent examples include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, ⁇ -terpinene, ⁇ -methylstyrene dimer, and the like.
- the temperature of emulsion polymerization can be appropriately set depending on the type of radical polymerization initiator used and the like, but is usually in the range of 0 to 100 ° C., preferably in the range of 0 to 60 ° C.
- the polymerization mode may be either continuous polymerization or batch polymerization.
- the polymerization reaction can be stopped by adding a polymerization terminator.
- the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite. After termination of the polymerization reaction, an antioxidant may be added as necessary.
- a salt such as sodium chloride, calcium chloride, potassium chloride is used as a coagulant, and nitric acid, sulfuric acid, etc.
- the polymerized product is solidified while adjusting the pH of the coagulation system to a predetermined value by adding an acid, and then the polymerized product is recovered by separating the dispersion solvent. Subsequently, after washing and dehydration, drying is performed to obtain an unmodified conjugated diene rubber.
- a latex and an extending oil previously made into an emulsified dispersion may be mixed and recovered as an oil-extended unmodified conjugated diene rubber.
- a known method or a method according to a known method can be applied. For example, using a Ziegler catalyst, a metallocene catalyst, an anion-polymerizable active metal or an active metal compound in a solvent, and a monomer containing a predetermined amount of a conjugated diene, if necessary, in the presence of a polar compound Is polymerized.
- the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Aromatic hydrocarbons such as toluene and xylene are exemplified.
- aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane
- alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane
- benzene Aromatic hydrocarbons such as toluene and xylene are exemplified.
- anion-polymerizable active metal examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium .
- alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
- an organic alkali metal compound is preferable.
- the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, dilithionaphthalene , 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, polyfunctional organolithium compounds such as 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like.
- organic alkali metal compounds organic lithium compounds are preferable, and organic monolithium compounds are more preferable.
- the amount of the organic alkali metal compound used can be appropriately set according to the melt viscosity, molecular weight, etc. of the unmodified conjugated diene rubber and the modified conjugated diene rubber, but with respect to 100 parts by mass of the total monomer containing the conjugated diene. Usually, it is used in an amount of 0.01 to 3 parts by mass.
- the organic alkali metal compound can be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, dibenzylamine or the like.
- Polar compounds are usually used in anionic polymerization to adjust the microstructure of the conjugated diene moiety without deactivating the reaction.
- the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
- the polar compound is usually used in an amount of 0.01 to 1000 mol with respect to the organoalkali metal compound.
- the temperature for solution polymerization is usually in the range of ⁇ 80 to 150 ° C., preferably in the range of 0 to 100 ° C., more preferably in the range of 10 to 90 ° C.
- the polymerization mode may be either batch or continuous.
- the polymerization reaction can be stopped by adding a polymerization terminator.
- the polymerization terminator include alcohols such as methanol and isopropanol.
- An unmodified conjugated diene rubber can be isolated by pouring the obtained polymerization reaction solution into a poor solvent such as methanol to precipitate a polymerized product, or washing the polymerization reaction solution with water, separating and drying.
- the solution polymerization method is preferable among the above methods.
- the modifying compound used in production method (1) is not particularly limited as long as it has a hydrogen bonding functional group.
- the hydrogen bonding functional group include the same ones as described above. Among these, amino group, imidazole group, urea group, hydroxy group, mercapto group, silanol group, aldehyde group, carboxyl group and derivatives thereof are preferable from the viewpoint of the strength of hydrogen bonding.
- As the derivative of the carboxyl group a salt thereof, an amidated product thereof, or an acid anhydride thereof is preferable.
- These modified compounds having a hydrogen bonding functional group may be used alone or in combination of two or more.
- Examples of the modifying compound include unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid and itaconic acid; and unsaturated carboxylic acids such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride and itaconic anhydride.
- Carboxylic anhydride unsaturated carboxylic acid ester such as maleic acid ester, fumaric acid ester, citraconic acid ester, itaconic acid ester; unsaturated carboxylic acid amide such as maleic acid amide, fumaric acid amide, citraconic acid amide, itaconic acid amide Unsaturated carboxylic acid imides such as maleic acid imide, fumaric acid imide, citraconic acid imide, and itaconic acid imide; vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyltriethoxysilane , 2-me Captoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethoxydimethylsilane, 2-mercaptoethylethoxydimethylsilane, 3-mercaptopropyltri
- the amount of the modifying compound used is preferably in the range of 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the unmodified conjugated diene rubber.
- the reaction temperature is usually preferably in the range of 0 to 200 ° C.
- a modified compound capable of reacting with the functional group is added to add another hydrogen-bonded functional group to the polymer. May be introduced.
- the addition amount of the modifying compound in the modified conjugated diene rubber is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and more preferably 1.5 to 20 parts per 100 parts by weight of the unmodified conjugated diene rubber. Part by mass is more preferable.
- the amount of the modified compound added to the modified conjugated diene rubber can also be calculated based on the acid value of the modified compound described later, and various analytical instruments such as infrared spectroscopy and nuclear magnetic resonance spectroscopy. It can also be obtained using.
- the method for adding the modified compound to the unmodified conjugated diene rubber is not particularly limited.
- a method of adding a radical generator and heating in the presence or absence of an organic solvent can be employed.
- the organic solvent used in the above method generally include hydrocarbon solvents and halogenated hydrocarbon solvents. Among these organic solvents, hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene and xylene are preferable.
- an anti-aging agent when performing the reaction which adds a modified compound by the said method, you may add an anti-aging agent from a viewpoint etc. which suppress a side reaction.
- the anti-aging agent commercially available products can be used, for example, butylated hydroxytoluene (BHT), N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (NOCRACK 6C), etc. Is mentioned.
- the addition amount of the antioxidant is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the unmodified conjugated diene rubber.
- the radical polymerizable compound having a hydrogen bonding functional group used in the production method (2) can be used without particular limitation as long as it is a compound having a hydrogen bonding functional group and a reactive multiple bond in the molecule.
- an aldehyde having a reactive multiple bond an acetalized product of the aldehyde; a monocarboxylic acid having a reactive multiple bond, a salt of the monocarboxylic acid, an esterified product of the monocarboxylic acid, the mono Dicarboxylic acid having a reactive multiple bond, salt of the dicarboxylic acid, esterified product of the dicarboxylic acid, acid anhydride of the dicarboxylic acid; and amine compound having a reactive multiple bond, etc.
- aldehydes having multiple bonds examples include acrolein, methacrolein, crotonaldehyde, 3-butenal, 2-methyl-2-butenal, 2-methyl-3.
- the acetals of aldehydes having reactive carbon-carbon double bonds include acetals of the aldehydes, specifically 2-methyl-3-butenal. Acetalized 3- (1,3-dioxalane-2-yl-)-3-methyl-1-propene and 3-methyl-3-butenal acetalized 3- (1,3-dioxalane- 2-yl) -2-methyl-1-propene and the like.
- an aldehyde having a reactive carbon-carbon triple bond and an acetalized product thereof include propiolualdehyde, 2-butyn-1-al, and 2-pentyne.
- Examples thereof include aldehydes having a carbon-carbon triple bond such as -1-al, and acetals of the aldehydes.
- an aldehyde having a reactive carbon-carbon double bond is preferable.
- At least one member selected from the enal are preferred. Among these, at least one selected from acrolein, metha
- Examples of the monocarboxylic acid having a multiple bond, a salt of the monocarboxylic acid, an esterified product of the monocarboxylic acid, and an acid anhydride of the monocarboxylic acid include (meth) acrylic acid and (meth) acrylic acid.
- Examples of the dicarboxylic acid having multiple bonds, the salt of the dicarboxylic acid, the esterified product of the dicarboxylic acid, and the acid anhydride of the dicarboxylic acid include maleic acid, sodium maleate, potassium maleate, maleic acid Reactive carbon-carbon double bonds such as methyl, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconate, dimethyl itaconate, itaconic anhydride, hymic acid, methyl hymic acid, dimethyl hymic acid, and hymic anhydride
- a dicarboxylic acid having a salt, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid include maleic acid, sodium maleate, potassium maleate, maleic acid Reactive carbon-carbon double bonds such as methyl, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconate
- esterified product and the acid anhydride of the dicarboxylic acid a compound having a reactive carbon-carbon double bond is preferable.
- methyl (meth) acrylate is preferable because of good reactivity during copolymerization.
- examples of the amine compound having a reactive carbon-carbon double bond include allylamine, 3-butenylamine, 4-pentenylamine, 5-hexenylamine, 6-heptenylamine, and 7-octenylamine.
- Oleylamine, 2-methylallylamine, 4-aminostyrene, 4-vinylbenzylamine, 2-allylglycine, S-allylcysteine, ⁇ -allylalanine, 2-allylaniline, geranylamine, vigabatrin, 4-vinylaniline, and 4-vinyloxyaniline and the like can be mentioned.
- one or more selected from allylamine, 3-butenylamine, and 4-pentenylamine is preferable because of good reactivity during copolymerization.
- a polymerized product of an unmodified conjugated diene monomer having a polymerization active terminal reacts with the polymerization active terminal before adding a polymerization terminator.
- the unmodified conjugated diene rubber having a polymerization active terminal is other than the conjugated diene monomer and, if necessary, other than the conjugated diene by, for example, an emulsion polymerization method or a solution polymerization method, as in the production method (1). It can obtain by polymerizing the monomer.
- Examples of the modifying compound that can be used in the production method (3) include dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate, carbon dioxide, ethylene oxide, succinic anhydride, 4,4'-bis (diethylamino) benzophenone, N-vinylpyrrolidone, N-methylpyrrolidone, 4-dimethylaminobenzylideneaniline, dimethylimidazolidinone And other modifiers described in JP-A No. 2011-132298.
- the amount of the modifying compound used is, for example, in the range of 0.01 to 100 molar equivalents relative to the organic alkali metal compound when polymerizing using an organic alkali metal compound.
- the reaction temperature is usually ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 90 ° C.
- another modifying compound capable of reacting with the functional group is added to add another hydrogen.
- a binding functional group may be introduced into the polymer.
- the modified conjugated diene rubber may contain a unit derived from another monomer other than the conjugated diene monomer and the radical polymerizable compound having a hydrogen bonding functional group as long as it does not inhibit adhesion.
- Other monomers include copolymerizable ethylenically unsaturated monomers and aromatic vinyl compounds. Examples of the ethylenically unsaturated monomer include olefins such as ethylene, 1-butene, and isobutylene.
- aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4 -Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2 -Vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinyl
- the modified conjugated diene rubber contains a monomer unit derived from the ethylenically unsaturated monomer and / or the aromatic vinyl compound, the content is preferably 30 mol% or less, and preferably 10 mol% or less. More preferred is 5 mol% or less.
- the weight average molecular weight (Mw) of the modified conjugated diene rubber is not particularly limited, but is preferably 200,000 or less, more preferably 120,000 or less, still more preferably 100,000 or less, and 75,000 from the viewpoint of handleability.
- the following is more preferable, 50,000 or less is particularly preferable, and from the viewpoint of improving adhesiveness, it is preferably more than 10,000, more preferably 20,000 or more, still more preferably 22,000 or more, 25,000 The above is even more preferable.
- the number average molecular weight (Mn) of the modified conjugated diene rubber is not particularly limited, but is preferably 200,000 or less, more preferably 120,000 or less, still more preferably 100,000 or less, and 75,000 from the viewpoint of handleability. The following is more preferable, 50,000 or less is particularly preferable, and from the viewpoint of improving adhesiveness, it is preferably more than 10,000, more preferably 20,000 or more, still more preferably 22,000 or more, 25,000 The above is even more preferable.
- Mw and Mn of the modified conjugated diene rubber are a weight average molecular weight and a number average molecular weight in terms of polystyrene determined from measurement by gel permeation chromatography (GPC).
- the molecular weight distribution (Mw / Mn) of the modified conjugated diene rubber is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, still more preferably 1.0 to 2.0, To 1.5 is even more preferable, and 1.0 to 1.3 is particularly preferable.
- the molecular weight distribution (Mw / Mn) means a ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement.
- the modified conjugated diene rubber is preferably liquid.
- “liquid” means that the melt viscosity of the modified conjugated diene rubber measured at 38 ° C. is 0.1 to 4,000 Pa ⁇ s.
- the melt viscosity is more preferably 1 to 2,000 Pa ⁇ s, still more preferably 1 to 1,000 Pa ⁇ s.
- the melt viscosity of the modified conjugated diene rubber is a value measured with a Brookfield viscometer at 38 ° C.
- the glass transition temperature (Tg) of the modified conjugated diene rubber can vary depending on the vinyl content of the conjugated diene unit, the type of conjugated diene, the content of units derived from other monomers other than the conjugated diene, and the like. 100 to 10 ° C is preferable, -100 to 0 ° C is more preferable, and -100 to -5 ° C is still more preferable. When Tg is in the above range, the increase in viscosity can be suppressed and handling becomes easy.
- the vinyl content of the modified conjugated diene rubber is preferably 99 mol% or less, and more preferably 90 mol% or less.
- the “vinyl content” means a conjugated diene unit bonded by 1,2-bond or 3,4-bond in a total of 100 mol% of conjugated diene units contained in the modified liquid diene rubber. It means the total mol% of (conjugated diene unit bonded other than 1,4-bond).
- the vinyl content is derived from a signal derived from a conjugated diene unit bonded by a 1,2-bond or a 3,4-bond and a conjugated diene unit bonded by a 1,4-bond using 1 H-NMR. It can be calculated from the integral value ratio of the signals.
- the modified conjugated diene rubber may be used alone or in combination of two or more.
- the adhesive component may contain other components other than the modified conjugated diene rubber as long as the adhesive force with the rubber is not impaired.
- the other components include other polymers (for example, unmodified conjugated diene rubber), acids, alkalis, antioxidants, curing agents, dispersants, pigments, dyes, adhesion aids, carbon black, and oil agents. .
- an oil agent mainly composed of unmodified conjugated diene rubber or mineral oil together with the modified conjugated diene rubber.
- the content of the other component is preferably 1 to 10,000 parts by mass, more preferably 30 parts, based on 100 parts by mass of the modified conjugated diene rubber, for example, when an unmodified conjugated diene rubber and / or an oil agent is included. It is ⁇ 5,000 parts by mass, more preferably 50 to 1,000 parts by mass. Further, the content of the modified conjugated diene rubber in the adhesive component is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, from the viewpoint of improving the adhesive strength with the rubber. And preferably 100% by mass or less.
- the reinforcing fiber of the present invention is a reinforcing fiber containing a hydrophilic fiber and an adhesive component, and has the adhesive component on at least a part of the surface of the hydrophilic fiber.
- hydrophilic fibers that can be used in the present invention include synthetic fibers, natural fibers, and regenerated fibers.
- a hydrophilic fiber may be used individually by 1 type, and may use 2 or more types together.
- the hydrophilic synthetic fiber is composed of a thermoplastic resin having a hydrophilic functional group such as a hydroxy group, a carboxyl group, a sulfonic acid group, and an amino group and / or a hydrophilic bond such as an amide bond. Mention may be made of synthetic fibers. Specific examples of such thermoplastic resins include polyvinyl alcohol resins, polyamide resins (polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 9C (polyamide comprising nonanediamine and cyclohexanedicarboxylic acid).
- Aliphatic polyamide such as polyamide 9T (polyamide composed of nonanediamine and terephthalic acid) and other semi-aromatic polyamides synthesized from aliphatic diamine and aliphatic diamine; aromatic dicarboxylic acid such as polyparaphenylene terephthalamide and aromatic A wholly aromatic polyamide synthesized from an aromatic diamine, etc.], a polyacrylamide resin and the like.
- polyvinyl alcohol resins and polyamide resins are preferable.
- One type of hydrophilic synthetic fiber may be used alone, or two or more types may be used in combination. Further, these hydrophilic synthetic fibers may be further subjected to a hydrophilization treatment described later in order to further increase the hydrophilicity.
- hydrophilic natural fibers include natural cellulose fibers such as wood pulp such as kraft pulp, and non-wood pulp such as cotton pulp and straw pulp.
- hydrophilic regenerated fibers include regenerated cellulose fibers such as rayon, lyocell, cupra, and polynosic. These natural fibers and regenerated fibers may be used alone or in combination of two or more. Moreover, these hydrophilic natural fibers and regenerated fibers may be further subjected to a hydrophilization treatment described later in order to further increase the hydrophilicity.
- the hydrophilic fiber only needs to have at least a hydrophilic surface, for example, a fiber obtained by hydrophilizing the surface of a hydrophobic fiber, or a core having a hydrophobic resin as a core and a sheath as a hydrophilic resin. It may be a sheath type composite fiber or the like. About the example of the hydrophilic resin which comprises a sheath part, the description about a hydrophilic synthetic fiber is quoted.
- the hydrophobic fiber made of a hydrophobic resin include polyolefin fibers such as polyethylene and polypropylene, polyester fibers such as polyethylene terephthalate, and wholly aromatic polyester fibers. Among these, polyester fibers are preferable. .
- the hydrophilization treatment is not particularly limited as long as it is a treatment that chemically or physically imparts a hydrophilic functional group to the fiber surface.
- the hydrophobic fiber made of the hydrophobic resin is converted into an isocyanate group, an epoxy group, and It can be carried out by a method of modifying with a compound containing a hydrophilic functional group such as a hydroxy group or a method of modifying the surface by electron beam irradiation.
- the hydrophilic fiber used in the present invention is preferably a synthetic fiber or a regenerated fiber from the viewpoint of being used as a reinforcing fiber, and in particular, the surface of a polyvinyl alcohol fiber, a regenerated cellulose fiber, or a hydrophobic fiber using a polyvinyl alcohol resin as a raw material.
- a fiber obtained by hydrophilizing is preferred.
- the modified conjugated diene rubber contained in the adhesive component and the hydrophilic fiber exhibit a strong affinity effect by using the hydrophilic fiber, and the adhesive component and the hydrophilic fiber are firmly bonded. The adhesive force with respect to can be made more excellent.
- polyvinyl alcohol fiber from the viewpoint of suitably using the reinforcing fiber of the present invention for an automobile hose, particularly an automobile brake oil hose, Kuraray Co., Ltd. is commercially available under the trade name “Vinylon” and has a single yarn fineness. Having a thickness of about 0.1 to 30 dtex can be preferably used.
- the method for producing the reinforcing fiber of the present invention is not particularly limited as long as it is a method in which the adhesive component is attached or contained in at least a part of the surface of the hydrophilic fiber.
- water, ethanol, propanol, butanol, methanol, toluene, xylene, acetone, hexane, tetrahydrofuran, methyl ethyl ketone, dioxane, tetrahydrofuran, and Ethyl acetate or the like may be used.
- the amount used is preferably 10 to 99.9% by mass, more preferably 40 to 99.9% by mass, and still more preferably 70 to 99.0% by mass in the total of the adhesive component and the solvent. It is.
- the method (I) for forming an adhesive layer comprising the adhesive component on the surface of the hydrophilic fiber, or the adhesive component as a part of the raw material is preferred.
- the method (I) is not particularly limited as long as it is a method for forming an adhesive layer composed of the adhesive component on the surface of the hydrophilic fiber, but from the viewpoint of improving the adhesiveness to rubber, the following step I-1 is performed. A method comprising is preferred. Step I-1: Step of attaching the adhesive component to the surface of the hydrophilic fiber
- the method for attaching the adhesive component to the hydrophilic fiber in Step I-1 there is no particular limitation on the method for attaching the adhesive component to the hydrophilic fiber in Step I-1.
- a method of adhering the modified conjugated diene rubber contained in the adhesive component as an oil-in-water emulsion
- a method of adhering the modified conjugated diene rubber dissolved in a solvent or a case where the modified conjugated diene rubber is liquid
- a method of adjusting the viscosity as needed and attaching it as it is can be mentioned.
- a method for adhering the adhesive component it is preferable to use one or more selected from dipping, roll coater, nozzle (spray) coating, brush coating, and the like.
- a drying process such as air drying.
- an emulsion (latex) of the adhesive component is prepared in advance by a mechanical or chemical method and used at a predetermined concentration by dilution or the like.
- a mechanical or chemical method examples include a homogenizer, a homomixer, a disperser mixer, a colloid mill, a pipeline mixer, a high-pressure homogenizer, and an ultrasonic emulsifier, and these can be used alone or in combination.
- Examples of the chemical method include various methods such as an inversion emulsification method, a D phase emulsification method, an HLB temperature emulsification method, a gel emulsification method, and a liquid crystal emulsification method, and the inversion emulsification method from the viewpoint of easily obtaining an emulsion having a small particle diameter. Is preferred.
- an inversion emulsification method a D phase emulsification method, an HLB temperature emulsification method, a gel emulsification method, and a liquid crystal emulsification method
- the inversion emulsification method from the viewpoint of easily obtaining an emulsion having a small particle diameter.
- the solid content is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
- emulsifiers fatty acid soaps such as potassium or sodium salts such as oleic acid, lauric acid, myristic acid, palmitic acid and stearic acid, resin soaps such as rosin and disproportionated rosin such as potassium or sodium salts, alkylbenzene sulfonic acid and alkyl Sulfonic acid soap such as sodium or potassium salt such as naphthalene sulfonic acid, sulfate ester soap such as sodium salt such as oleyl sulfate ester, lauryl sulfate ester, polyoxyethylene alkyl sulfate ester, hexadecyl phosphate, polyoxyethylene lauryl ether phosphate Fate, polyoxyethylene tridecyl ether phosphate, anion soap such as polyoxy
- the amount of the emulsifier used is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the modified conjugated diene rubber. If the amount of the emulsifier used is less than or equal to the above upper limit, the use of an excess emulsifier can be suppressed without affecting the stability of the emulsion, which is economically advantageous and the adhesive strength and the like are improved. Moreover, when the usage-amount of this emulsifier is more than the said minimum, the increase in an emulsion particle diameter can be suppressed and generation
- the emulsion particle diameter is preferably adjusted to 0.1 to 8 ⁇ m, more preferably 0.1 to 5 ⁇ m, and still more preferably 0.1 to 1 ⁇ m.
- an alkaline substance such as sodium hydroxide, potassium hydroxide or amines may be added as necessary to adjust the pH.
- the adhesion amount of the adhesive component is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 1% by mass with respect to the reinforcement fiber from the viewpoint of improving the adhesion between the reinforcement fiber and rubber.
- the above is more preferable, and 10% by mass or less is preferable and 5% by mass or less is more preferable from the viewpoint of the balance between the manufacturing cost and the effect.
- Step I-2 A step of heat-treating the hydrophilic fiber to which the adhesive component obtained in Step I-1 is attached.
- the heat treatment in Step I-2 is preferably performed at a treatment temperature of 100 to 200 ° C. for 0.1 seconds to 2 It is preferable to carry out with a processing time of minutes. Since the modified conjugated diene rubber contained in the adhesive component has reactive multiple bonds, the heat treatment in the presence of oxygen is preferably 200 ° C. or lower, and more preferably 175 ° C. or lower.
- the adhesive strength can be improved without reducing the amount of reactive multiple bonds in the modified conjugated diene rubber, and further the deterioration of the fibers is suppressed, and the quality such as coloring is improved. Will also be good.
- the method for producing a reinforcing fiber of the present invention may be a method (II) for producing a fiber containing the adhesive component as a part of the raw material.
- the raw material other than the adhesive component when the reinforcing fiber contains the adhesive component as a part of the raw material there is no particular limitation on the raw material other than the adhesive component when the reinforcing fiber contains the adhesive component as a part of the raw material.
- the content of the adhesive component in the fiber raw material is preferably 5% by mass or more from the viewpoint of improving the adhesion between the reinforcing fiber and the rubber, 10 mass% or more is more preferable, 30 mass% or more is still more preferable, and 70 mass% or less is preferable from a viewpoint of the balance of manufacturing cost and an effect, 65 mass% or less is more preferable, and 50 mass% or less is still more. preferable.
- the production method of the fiber is not particularly limited, and can be produced according to a general synthetic fiber production method.
- a method in which polyvinyl alcohol having a polymerization degree of 1,500 or more and a saponification degree of 99 mol% or more and the adhesive component are dissolved or semi-melted in water or an organic solvent, and wet, dry or dry-wet spinning is used.
- the reinforcing fiber may contain components other than the hydrophilic fiber and the adhesive component.
- other components include a crosslinking agent, an acid, a base, an inorganic salt, an organic salt, a pigment, a dye, an antioxidant, a polymerization initiator, and a plasticizer.
- the total content of the hydrophilic fiber and the adhesive component in the reinforcing fiber is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably, from the viewpoint of improvement in adhesive strength with rubber and reinforcement strength. Is 95% by mass or more.
- the reinforcing fiber is preferably a multifilament having a single yarn fineness of 0.1 dtex to 30 dtex.
- the single yarn fineness may be less than 0.1 dtex, but is preferably 0.1 dtex or more because it is difficult to produce industrially. Further, when the single yarn fineness is 30 dtex or less, the surface area of the fiber in the case of the reinforcing fiber is increased, and thus the adhesiveness to the rubber is improved.
- the reinforcing fiber of the present invention has a single yarn fineness of preferably 0.3 dtex or more, more preferably 0.5 dtex or more, still more preferably 1 dtex or more, and more preferably 20 dtex or less, and still more preferably. Is preferably a multifilament of 15 dtex or less, more preferably 10 dtex or less.
- the initial tensile resistance measured according to JIS L 1013: 2010 is preferably 60 cN / dtex or more.
- the initial tensile resistance of the reinforcing fiber is 60 cN / dtex or more, the reinforcing strength when the reinforcing fiber and rubber are bonded is improved.
- the initial tensile resistance is more preferably 100 cN / dtex or more, further preferably 130 cN / dtex or more, still more preferably 160 cN / dtex or more, and particularly preferably 200 cN / dtex or more.
- it is 1,000 cN / dtex or less.
- the reinforcing fiber of the present invention can be used in an arbitrary shape, but is preferably used in the form of a fiber cord, a woven fabric, a knitted fabric or the like containing at least a part of the reinforcing fiber. It is more preferable to use it as a woven or knitted fabric included in the part. For example, it can be used as a knitted fabric that adheres to rubber as described later. It can also be used as a reinforcing fiber embedded in resin or cement.
- the shaped product of the present invention is not particularly limited as long as the reinforcing fiber is used.
- a molded body using the reinforcing fiber and a rubber component (hereinafter, also referred to as “rubber molded body”) is preferable because the reinforcing fiber has excellent adhesiveness with rubber.
- the reinforcing fiber used in the rubber molded body is preferably used as a woven fabric or a knitted fabric containing at least a part of the reinforcing fiber from the viewpoint of maintaining the shape of the rubber. More preferably, it is used as a laminate in which a reinforcing layer made of a knitted fabric and a rubber layer are laminated.
- the rubber molded body can be used as a member of a rubber product such as a tire such as an automobile tire, a belt such as a conveyor belt or a timing belt, a hose, and an anti-vibration rubber. It is more preferable to use as.
- the automobile tire can be used for various members made of a composite material of a reinforcing fiber and a rubber component such as a belt, a carcass ply, a breaker, and a bead tape.
- the hose can be used for the purpose of transporting various fluids in various applications.
- the hose is suitable for a fluid transport hose for automobiles, and in particular, a liquid fuel hose for automobiles and a brake for automobiles. It is preferably used for an oil hose and a refrigerant hose, and more preferably used for an automobile brake oil hose.
- the rubber molded body is preferably molded using the reinforcing fiber and a rubber composition in which a rubber component is blended with a compounding agent usually used in the rubber industry.
- the rubber component is not particularly limited.
- NR natural rubber
- IR polyisoprene rubber
- BR polybutadiene rubber
- SBR styrene-butadiene rubber
- NBR nitrile rubber
- EPM ethylene- Propylene copolymer rubber
- EPDM ethylene-propylene-nonconjugated diene copolymer rubber
- IIR butyl rubber
- halogenated butyl rubber CR (chloroprene rubber) and the like.
- NR, IR, BR, SBR, EPDM, and CR are preferably used, and EPDM is more preferably used.
- These rubber components may be used alone or in combination of two or more. In tire applications, those generally used in the tire industry can be used. Among these, it is preferable to use natural rubber alone or a combination of natural rubber and SBR.
- the mass ratio of natural rubber to SBR is in the range of 50/50 to 90/10 from the viewpoint of suppressing physical property degradation due to reversion of rubber. It is preferable to do.
- the natural rubber is generally used in the tire industry such as SMR (Malaysia TSR), SIR (Indonesia TSR), STR (Thailand TSR), etc.
- TSR Technically Specified Rubber
- RSS Rabbed Smoked Sheet
- modified natural rubber such as natural rubber, high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, and grafted natural rubber.
- the SBR a general one used for tires can be used.
- the styrene content is preferably 0.1 to 70% by mass, more preferably 5 to 50% by mass, More preferred is 15 to 35% by mass.
- the vinyl content is preferably 0.1 to 60% by mass, more preferably 0.1 to 55% by mass.
- the weight average molecular weight (Mw) of the SBR is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and 200,000 to 1,500,000. More preferably. When it is in the above range, both workability and mechanical strength can be achieved.
- the weight average molecular weight of SBR is a weight average molecular weight in terms of polystyrene determined from measurement by gel permeation chromatography (GPC).
- modified SBR in which a functional group is introduced into SBR may be used as long as the effects of the present invention are not impaired.
- the functional group include an amino group, an alkoxysilyl group, a hydroxy group, an epoxy group, and a carboxyl group.
- the rubber composition may further contain a filler in addition to the rubber component.
- a filler examples include inorganic fillers such as carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, fibrous filler, and glass balloon; resin particles, Organic fillers such as wood powder and cork powder are listed.
- inorganic fillers such as carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, fibrous filler, and glass balloon
- resin particles Organic fillers such as wood powder and cork powder are listed.
- carbon black and silica are preferable from the viewpoint of improving physical properties such as improvement of mechanical strength.
- the carbon black examples include furnace black, channel black, thermal black, acetylene black, and ketjen black. Of these carbon blacks, furnace black is preferable from the viewpoint of improving the crosslinking speed and mechanical strength.
- the average particle size of the carbon black is preferably 5 to 100 nm, more preferably 5 to 80 nm, and still more preferably 5 to 70 nm.
- the average particle size of the carbon black can be obtained by measuring the particle diameter with a transmission electron microscope and calculating the average value.
- silica examples include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate. Among these silicas, wet silica is preferable.
- the average particle diameter of the silica is preferably 0.5 to 200 nm, more preferably 5 to 150 nm, and still more preferably 10 to 100 nm. The average particle diameter of the silica can be determined by measuring the diameter of the particles with a transmission electron microscope and calculating the average value.
- the filler content relative to 100 parts by mass of the rubber component is preferably 20 to 150 parts by mass, more preferably 25 to 130 parts by mass, and still more preferably 25 to 110 parts by mass.
- the content thereof is preferably 20 to 120 parts by mass, more preferably 20 to 90 parts by mass with respect to 100 parts by mass of the rubber component. 20 to 80 parts by mass is more preferable.
- the rubber composition may further contain a crosslinking agent in order to crosslink the rubber component.
- a crosslinking agent examples include sulfur, sulfur compounds, oxygen, organic peroxides, phenol resins, amino resins, quinones and quinonedioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides and organic compounds. Examples thereof include metal halides and silane compounds.
- These crosslinking agents may be used alone or in combination of two or more.
- the crosslinking agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 0.8 to 5 parts by weight with respect to 100 parts by weight of the rubber component from the viewpoint of mechanical properties of the crosslinked product. Contained in parts by mass.
- the rubber composition may further contain a vulcanization accelerator when sulfur, a sulfur compound, or the like is included as a crosslinking agent for crosslinking (vulcanizing) the rubber component.
- a vulcanization accelerator examples include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds, aldehyde-ammonia compounds, imidazolines. And xanthate compounds.
- These vulcanization accelerators may be used alone or in combination of two or more.
- the vulcanization accelerator is usually contained in an amount of 0.1 to 15 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component.
- the rubber composition may further contain a vulcanization aid, for example, when sulfur, a sulfur compound or the like is included as a crosslinking agent for crosslinking (vulcanizing) the rubber component.
- a vulcanization aid for example, when sulfur, a sulfur compound or the like is included as a crosslinking agent for crosslinking (vulcanizing) the rubber component.
- the vulcanization aid include fatty acids such as stearic acid, metal oxides such as zinc white, and fatty acid metal salts such as zinc stearate. These vulcanization aids may be used alone or in combination of two or more.
- the vulcanization aid is usually contained in an amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the rubber component.
- the rubber composition contains silica as a filler, it is preferable to further contain a silane coupling agent.
- the silane coupling agent include sulfide compounds, mercapto compounds, vinyl compounds, amino compounds, glycidoxy compounds, nitro compounds, chloro compounds, and the like. These silane coupling agents may be used alone or in combination of two or more.
- the silane coupling agent is contained in an amount of preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass with respect to 100 parts by mass of silica. When the content of the silane coupling agent is within the above range, dispersibility, coupling effect, and reinforcing properties are improved.
- the rubber composition is intended to improve processability, fluidity and the like within a range that does not impair the effects of the present invention, and if necessary, silicon oil, aroma oil, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted) Solvates), RAE (Residual Aromatic Extracts), paraffin oil, naphthenic oil and other process oils, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9 resins, rosin resins, coumarone / indene resins, phenol resins, etc. These resin components may be contained as a softening agent. When the rubber composition contains the process oil as a softening agent, the content is preferably less than 50 parts by mass with respect to 100 parts by mass of the rubber component.
- the rubber composition is an anti-aging agent, a wax, an antioxidant, a lubricant, a light stabilizer, if necessary, for the purpose of improving the weather resistance, heat resistance, oxidation resistance, etc. within the range that does not impair the effects of the present invention.
- additives such as fragrances may be contained.
- the antioxidant include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxyl compounds, and the like.
- the antiaging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds, and phosphorus compounds. These additives may be used alone or in combination of two or more.
- the reinforcing fiber is embedded in the unvulcanized rubber composition, and the rubber composition is vulcanized so that the hydrophilic fiber and the rubber component are bonded to each other.
- a molded body bonded through the components can be obtained.
- the automobile brake oil hose has, for example, an inner rubber layer and an outer rubber layer, and a reinforcing layer made of one or two reinforcing fibers between the inner rubber layer and the outer rubber layer. Things. Examples of the rubber component constituting the inner rubber layer and the outer rubber layer include those described above. Especially, EPDM, SBR, etc. are mentioned as a rubber component which comprises an inner side rubber layer, EPDM, CR, etc. are mentioned as a rubber component which comprises an outer side rubber layer.
- the reinforcing layer can be formed by braiding reinforcing fibers. As a method for manufacturing the brake oil hose, a reinforcing layer (first reinforcing layer) formed by braiding the reinforcing fibers is formed on the outer surface of the inner rubber layer.
- an intermediate rubber layer is further formed on the outer surface of the first reinforcing layer, and the reinforcing fiber braided on the outer surface of the intermediate rubber layer (second layer).
- (Reinforcing layer) may be formed. And it can manufacture by forming an outer side rubber layer on the outer surface of a reinforcement layer (a 1st reinforcement layer or a 2nd reinforcement layer), and vulcanizing
- the vulcanization temperature can be appropriately selected depending on the type of constituent material of each layer of the brake oil hose, etc., but from the viewpoint of suppressing the deterioration of the rubber and the reinforcing fiber and improving the adhesive force between the rubber and the reinforcing fiber, it is 200 ° C. or less. Preferably there is.
- Production Example 1 Production of Modified Conjugated Diene Rubber (A-1) A well-dried 5 L autoclave was purged with nitrogen, charged with 1200 g of hexane and 26.2 g of n-butyllithium (17% by mass hexane solution), and heated to 50 ° C. After the temperature was raised, 1200 g of isoprene was sequentially added and polymerized for 1 hour while controlling the polymerization temperature to be 50 ° C. under stirring conditions. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the resulting polymer solution and stirred, and the polymer solution was washed with water.
- A-1 A well-dried 5 L autoclave was purged with nitrogen, charged with 1200 g of hexane and 26.2 g of n-butyllithium (17% by mass hexane solution), and heated to 50 ° C. After the temperature was raised, 1200 g of iso
- Production Example 2 Production of Modified Conjugated Diene Rubber (A-2) Unmodified liquid polyisoprene (A′-1) obtained in the same procedure as in Production Example 1 in a 1 L autoclave subjected to nitrogen substitution 500 g was charged, 7.5 g of maleic anhydride and 0.5 g of butylated hydroxytoluene (BHT) were added and reacted at 170 ° C. for 15 hours to obtain maleic anhydride-modified liquid polyisoprene (A-2).
- A-2 Modified Conjugated Diene Rubber
- Production Example 3 Production of Modified Conjugated Diene Rubber (A-3) Unmodified liquid polyisoprene (A′-1) obtained in the same procedure as in Production Example 1 in a 1 L autoclave subjected to nitrogen substitution 500 g was charged, 50 g of maleic anhydride and 0.5 g of butylated hydroxytoluene (BHT) were added and reacted at 170 ° C. for 15 hours to obtain maleic anhydride-modified liquid polyisoprene (A-3).
- A-3 Modified Conjugated Diene Rubber
- Production Example 4 Production of Modified Conjugated Diene Rubber (A-4) A well-dried 5 L autoclave was purged with nitrogen, charged with 1260 g of hexane and 36.3 g of n-butyllithium (17% by mass hexane solution), and heated to 50 ° C. After raising the temperature, 1260 g of butadiene was successively added and polymerized for 1 hour while controlling the polymerization temperature to be 50 ° C. under stirring conditions. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the resulting polymer solution and stirred, and the polymer solution was washed with water.
- Production Example 5 Production of Modified Conjugated Diene Rubber (A-5) 500 g of unmodified liquid polybutadiene (A′-2) obtained in the same procedure as in Production Example 3 in a 1 L autoclave subjected to nitrogen substitution. Then, 37 g of 3-mercaptopropyltriethoxysilane and 0.5 g of butylated hydroxytoluene (BHT) were added and reacted at 105 ° C. for 8 hours to obtain triethoxysilane-modified liquid polybutadiene (A-5).
- BHT butylated hydroxytoluene
- Production Example 6 Production of modified conjugated diene rubber (A-6) having a structural unit derived from ⁇ -farnesene monomer A sufficiently dried 5 L autoclave was purged with nitrogen, 1200 g of hexane and n-butyllithium (17 mass) % Hexane solution) was charged, and the temperature was raised to 50 ° C., and then 1200 g of ⁇ -farnesene was sequentially added under polymerization conditions while controlling the polymerization temperature to 50 ° C., and polymerized for 1 hour. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the resulting polymer solution and stirred, and the polymer solution was washed with water.
- a sufficiently dried 5 L autoclave was purged with nitrogen, 1200 g of hexane and n-butyllithium (17 mass) % Hexane solution) was charged, and the temperature was raised to 50 ° C., and then 1200
- Production Example 7 Production of Modified Conjugated Diene Rubber (A-7) Having Structural Units Derived from ⁇ -Farnesene Monomer and Butadiene Monomer
- a sufficiently dried 5 L autoclave was purged with nitrogen, and 1200 g of hexane and sec- Charge 32.8 g of butyllithium (10.5 mass% cyclohexane solution), raise the temperature to 50 ° C., and control ⁇ -farnesene and butadiene prepared in advance under stirring conditions while controlling the polymerization temperature to 50 ° C.
- each physical property such as a modified conjugated diene rubber
- the results are shown in Table 1. (Method for measuring weight average molecular weight, number average molecular weight and molecular weight distribution) Mw, Mn, and Mw / Mn of the modified conjugated diene rubber were obtained as standard polystyrene conversion values by GPC (gel permeation chromatography).
- the measuring apparatus and conditions are as follows.
- GPC device GPC device “GPC8020” manufactured by Tosoh Corporation Separation column: “TSKgel G4000HXL” manufactured by Tosoh Corporation ⁇ Detector: “RI-8020” manufactured by Tosoh Corporation ⁇ Eluent: Tetrahydrofuran ⁇ Eluent flow rate: 1.0 ml / min ⁇ Sample concentration: 5 mg / 10 ml -Column temperature: 40 ° C
- melt viscosity The melt viscosity of the modified conjugated diene rubber at 38 ° C. was measured with a Brookfield viscometer (manufactured by BROOKFIELD ENGINEERING LABS. INC.).
- the average number of hydrogen bonding functional groups per molecule of the modified conjugated diene rubber was calculated from the following formula from the equivalent (g / eq) of hydrogen bonding functional groups of the modified conjugated diene rubber and the number average molecular weight Mn in terms of styrene. .
- Average number of hydrogen bonding functional groups per molecule [(Number average molecular weight (Mn)) / (Molecular weight of styrene unit) ⁇ (Average of monomer units other than conjugated diene and conjugated diene contained as necessary) Molecular weight)] / (equivalent of hydrogen bonding functional group)
- the calculation method of the equivalent of a hydrogen bondable functional group can be suitably selected according to the kind of hydrogen bondable functional group.
- the equivalent of hydrogen-bonding functional groups in the calculation of the average number of hydrogen-bonding functional groups per molecule of triethoxysilane-modified conjugated diene rubber is derived from hydrogen-bonding functional groups using 1 H-NMR or 13 C-NMR. It calculated from the integral value ratio of a signal and the signal originating in a polymer principal chain.
- the signal derived from a hydrogen bonding functional group means a signal derived from an alkoxy group in the case of triethoxysilane-modified conjugated diene rubber.
- the calculation of the average number of hydrogen-bonding functional groups per molecule of maleic anhydride-modified conjugated diene rubber is obtained by obtaining the acid value of maleic anhydride-modified conjugated diene rubber and calculating the equivalent (g / Eq).
- the sample after the denaturation reaction was washed 4 times with methanol (5 mL with respect to 1 g of the sample) to remove impurities such as antioxidants, and then the sample was dried under reduced pressure at 80 ° C. for 12 hours.
- Acid value (mgKOH / g) (AB) ⁇ F ⁇ 5.661 / S A: A drop amount of ethanol solution of 0.1N potassium hydroxide required for neutralization (mL) B: 0.1N potassium hydroxide ethanol solution drop volume in a blank containing no sample (mL) F: Potency of ethanol solution of 0.1N potassium hydroxide S: Weight of sample weighed (g)
- the mass of hydrogen-bonding functional groups contained per gram of maleic anhydride-modified conjugated diene rubber is calculated from the following formula, and the mass other than the functional groups contained per gram of maleic anhydride-modified conjugated diene rubber. (Polymer main chain mass) was calculated. And the equivalent (g / eq) of the hydrogen bondable functional group was computed from the following formula
- Phosphanol RS-710 ether phosphate Fate
- Phosphanol RS-710 trade name “Phosphanol RS-710”, manufactured by
- Phosphanol RS-710 ether phosphate.
- the adhesion amount of the adhesive component was measured by the following measuring method. About 10 g of reinforcing fiber was sampled and its mass X was measured. The adhesive component was extracted from the sample, and the extracted mass Y was measured. For extraction, toluene was used as a solvent, and extraction was performed with a Soxhlet extractor for 3 hours. The adhesion amount of the adhesive component was calculated by the following formula.
- Adhesion amount of adhesive component to reinforcing fiber (Y / X) ⁇ 100
- the content (mass%) of the modified conjugated diene rubber in the adhesive component was calculated from the mass ratio of the modified conjugated diene rubber in the solid content of the adhesive component.
- Example 1 As Example 1, a reinforcing fiber having an adhesive layer composed of an adhesive component on at least a part of the surface of the hydrophilic fiber was produced and evaluated as follows.
- the adhesive component made of the modified conjugated diene rubber (A-1) produced as described above was dissolved in tetrahydrofuran so that the solid content concentration was 4% by mass.
- a vinylon fiber (Kuraray Co., Ltd. “KURALON 1239”, total fineness 1330 dtex, single yarn fineness 6.65 dtex) manufactured by Kuraray Co., Ltd. as a hydrophilic fiber was immersed in this solution, and then pulled up and air-dried in a draft. .
- the fiber cord was produced by twisting the vinylon to which the adhesive component was adhered in this way at a twist number of 80 T / m.
- reinforcing fibers having an adhesive layer made of an adhesive component on at least a part of the surface of the hydrophilic fiber were produced and evaluated as follows.
- Adhesive components composed of the modified conjugated diene rubber emulsions (E-1) to (E-7) produced as described above were each dispersed in water so that the solid concentration was 4% by mass.
- Vinylon fibers ("Kuraray 1239" manufactured by Kuraray Co., Ltd., total fineness 1330 dtex, single yarn fineness 6.65 dtex) were immersed in this dispersion, and then squeezed with a roller. Next, the obtained fiber was dried at 120 ° C. for 30 seconds and heat treated at 170 ° C. for 30 seconds.
- the fiber cord was produced by twisting the vinylon to which the adhesive component was adhered in this way at a twist number of 80 T / m.
- Comparative Example 1 a fiber cord was produced in the same manner as in Example 1 except that unmodified conjugated diene rubber (A′-1) was used as an adhesive component.
- A′-1 unmodified conjugated diene rubber
- Example 2 was used except that PET fiber (“702C” manufactured by Toray Industries, Inc., total fineness 1670 dtex, single yarn fineness 5.80 dtex), which is a hydrophobic polyester fiber, was used instead of the vinylon fiber.
- PET fiber 702C manufactured by Toray Industries, Inc., total fineness 1670 dtex, single yarn fineness 5.80 dtex
- a fiber cord was produced in the same manner as described above.
- Reference Example 1 a known RFL treatment was applied to vinylon fiber (“Kuraron 1239” manufactured by Kuraray Co., Ltd., total fineness 1330 dtex, single yarn fineness 6.65 dtex) so that the adhesion amount was 3.0 mass%.
- the fiber cord was produced by twisting the vinylon to which the adhesive component was adhered in this way at a twist number of 80 T / m.
- the RFL solution used was prepared by the following method.
- EPDM rubber 100 parts by weight Filler (carbon black): 60 parts by weight Softener (paraffinic process oil): 20 parts by weight Cross-linking agent (sulfur powder): 1.5 parts by weight Vulcanization aid (two types of zinc white, stearin) Acid): 6 parts by mass Vulcanization accelerator (thiazole type, thiuram type): 1.5 parts by mass
- the initial tensile resistance of the obtained evaluation sheet was measured according to JIS L 1013: 2010 using a measuring machine (Instron 3365). A peeling test was performed by moving 200 mm at a peeling speed of 50 mm / min, and the fiber cord and the rubber were peeled off. The maximum value of 5 points and 5 points are taken out from a number of peaks appearing in the range excluding 10 mm from the first peak and 10 mm from the last peak, and the average value is taken as the initial tensile resistance of the fiber and rubber. . In addition, the value was extract
- Example 9 is the same as Example 1 except that a rayon fiber (“Cordenka 700” manufactured by Cordenka, total fineness 1840 dtex, single yarn fineness 1.84 dtex), which is a regenerated cellulosic fiber, was used as the hydrophilic fiber instead of vinylon fiber.
- a fiber cord was produced in the same manner as described above.
- Example 10 a PET fiber (“702C” manufactured by Toray Industries, Inc., total fineness 1670 dtex, single yarn fineness 5.80 dtex), which is a polyester fiber subjected to the hydrophilization treatment described later, was used as the hydrophilic fiber.
- a fiber cord was produced in the same manner as in Example 1.
- Comparative Example 3 is Comparative Example 1 except that a rayon fiber (“Cordenka 700” manufactured by Cordenka, total fineness of 1840 dtex, single yarn fineness of 1.84 dtex), which is a regenerated cellulose fiber, was used as the hydrophilic fiber instead of vinylon fiber.
- a fiber cord was produced in the same manner as described above.
- Comparative example 4 a PET fiber (“702C” manufactured by Toray Industries, Inc., total fineness 1670 dtex, single yarn fineness 5.80 dtex), which is a polyester fiber subjected to the hydrophilization treatment described later, was used as the hydrophilic fiber.
- a fiber cord was produced in the same manner as in Comparative Example 1.
- Reference Example 2 produced a fiber cord in the same manner as Reference Example 1 except that rayon fiber (“Cordenka 700” manufactured by Cordenka, 1840 dtex), which is a regenerated cellulosic fiber, was used as the hydrophilic fiber instead of vinylon fiber. did.
- Reference Example 3 is a polyester fiber that has been subjected to a hydrophilization treatment described later as a hydrophilic fiber, except that PET fiber ("702C” manufactured by Toray Industries, Ltd., total fineness 1670 dtex, single yarn fineness 5.80 dtex) is used. A fiber cord was produced in the same manner as in Reference Example 1.
- PET fibers (“702C” manufactured by Toray Industries, Inc., total fineness 1670 dtex, single yarn fineness 5.80 dtex), which are polyester fibers, were immersed in an aqueous solution adjusted to the following composition, and then squeezed with a roller. Next, the obtained fiber was dried at 130 ° C. for 60 seconds, and further heat treated at 240 ° C. for 60 seconds and wound up to produce a hydrophilically treated PET fiber.
- composition of hydrophilic treatment agent Water: 96.96 parts by weight Meika Note DM-3031 CONC: 22 parts by weight Denacol EX-614B: 7 parts by weight
- the hydrophilic treatment agent was prepared using blocked isocyanate and an epoxy resin. Note that “Meikanaut DM-3031 CONC” manufactured by Meisei Chemical Co., Ltd. was used as the blocked isocyanate, and “Denacol EX-614B” manufactured by Nagase ChemteX Corporation was used as the epoxy resin.
- the reinforcing fiber of the present invention obtains a reinforcing fiber excellent in adhesion to rubber without using an adhesive mainly composed of resorcin / formalin resin and rubber latex. be able to.
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Abstract
Description
具体的に、特許文献3には、ゴムの加硫に用いられる加硫剤と反応する不飽和炭素結合及びエポキシ基を有する接着化合物を含む接着剤を用いる技術が提案されている。特許文献4には、(ブロックド)イソシアネート化合物及び/又はアミン系硬化剤(A)と、エポキシ化合物(B)と、ゴムラテックス(C)と、を含み、レゾルシン及びホルマリンを含まない有機繊維コード用接着剤組成物を用いた接着方法が提案されている。特許文献5には、液状ゴムが付着したゴム補強用繊維として、機械的せん断力により分割・細径化する技術が提案されている。
特許文献4に記載された接着剤を用いた方法は、従来のRFLを用いた方法と同等かそれ以上の接着力を有するものの、有機繊維コードの表面に接着剤層を形成した後、実質的には高温(180℃及び240℃)によって加熱処理する必要があった。補強繊維としてしばしば用いられるPVA系繊維やPET系繊維といった有機繊維をかかる方法で処理した場合、劣化によって補強繊維としての性能が落ちる危険性があった。また、特許文献5に記載された技術は、ゴム補強用繊維を機械的せん断力により分割・細径化し、ゴム成型体の製造で用いるマトリックス・ゴムの基本性能を損なうことなく優れた分散性及び補強性を向上させる技術であるが、ゴムとの接着力においては更なる改善が求められていた。
そこで、従来のRFLを用いた方法と同程度の接着力を有しながら、汎用的な繊維が劣化しない接着方法が求められていた。
[1]親水性繊維及び接着成分を含有する補強繊維であって、
該親水性繊維の表面の少なくとも一部に該接着成分を有し、
該接着成分が、共役ジエン系ゴムの一部に水素結合性官能基を有する変性共役ジエン系ゴムを含み、かつ、該変性共役ジエン系ゴム中の水素結合性官能基数が1分子当たりの平均で2~150個である、補強繊維。
[2]前記[1]に記載の補強繊維の製造方法。
[3]前記[1]に記載の補強繊維を用いた、成形体。
本発明の補強繊維は、親水性繊維及び接着成分を含有する補強繊維であって、該親水性繊維の表面の少なくとも一部に該接着成分を有し、該接着成分が、共役ジエン系ゴムの一部に水素結合性官能基を有する変性共役ジエン系ゴム(以下、「変性共役ジエン系ゴム」とも称する)を含み、かつ、該変性共役ジエン系ゴム中の水素結合性官能基数が1分子当たりの平均で2~150個である。本発明によれば、変性共役ジエン系ゴムが親水性繊維の表面の少なくとも一部に存在することで、補強繊維とゴムとの濡れ性が改善され、かつ該変性共役ジエン系ゴムの有する多重結合とゴム等とが反応し結合を形成するため、優れた接着力を有する補強繊維を得ることができる。
なお、本発明において、前記接着成分は、前記親水性繊維中に含まれていてもよいが、該親水性繊維の表面の少なくとも一部には存在するものである。
本発明において用いる接着成分は、共役ジエン系ゴムの一部に水素結合性官能基を有する変性共役ジエン系ゴムを含み、かつ、該変性共役ジエン系ゴム中の水素結合性官能基数が1分子当たりの平均で2~150個であれば特に制限はない。本発明によれば、変性共役ジエン系ゴムが被着体であるゴム及び親水性繊維のそれぞれと相互作用することによって、両者を接着させる。変性共役ジエン系ゴムは少なくとも一部に被着ゴムと似た分子構造を有するため、分子鎖が絡み合い相互作用する。また、変性共役ジエン系ゴムと被着ゴムは加硫によって共有結合を形成することで強い凝集力が生じ、接着性が向上する。更に、変性共役ジエン系ゴムに含まれる水素結合性官能基が親水性繊維と水素結合を中心とした相互作用をすることにより接着性が向上すると考えられる。
ここで、「水素結合」とは、電気陰性度の大きな原子(O、N、S等)に結合し、電気的に陽性に分極した水素原子(ドナー)と、孤立電子対を有する電気的に陰性な原子(アクセプター)との間に形成される結合性の相互作用を意味する。
変性共役ジエン系ゴム1分子当たりの平均水素結合性官能基数は、変性共役ジエン系ゴムの水素結合性官能基の当量(g/eq)とスチレン換算の数平均分子量Mnから、下記式に基づき算出される。変性共役ジエン系ゴムの水素結合性官能基の当量は、水素結合性官能基1個当たりに結合している共役ジエン及び必要に応じて含まれる共役ジエン以外の他の単量体の質量を意味する。
1分子当たりの平均水素結合性官能基数=[(数平均分子量(Mn))/(スチレン単位の分子量)×(共役ジエン及び必要に応じて含まれる共役ジエン以外の他の単量体単位の平均分子量)]/(水素結合性官能基の当量)
なお、水素結合性官能基の当量の算出方法は、水素結合性官能基の種類により適宜選択することができる。
前記共役ジエン単量体としては、例えば、ブタジエン、2-メチル-1,3-ブタジエン(以下、「イソプレン」とも称する)、2,3-ジメチルブタジエン、2-フェニルブタジエン、1,3-ペンタジエン、2-メチルー1,3-ペンタジエン、1,3-ヘキサジエン、1,3-オクタジエン、1,3-シクロヘキサジエン、2-メチル-1,3-オクタジエン、1,3,7-オクタトリエン、ミルセン、β-ファルネセン、α-ファルネセン及びクロロプレン等が挙げられる。これら共役ジエンは、1種単独で用いてもよく、2種以上を併用してもよい。変性共役ジエン系ゴムは、加硫時の反応性の観点から、分子内にブタジエン及びイソプレンから選ばれる1種以上に由来する単量体単位を有することが好ましく、ブタジエンに由来する単量体単位を有することがより好ましい。
製造方法(1)は、共役ジエン単量体の重合化物、すなわち未変性の共役ジエン系ゴム(以下、「未変性共役ジエン系ゴム」とも称する)に変性化合物を付加する方法である。
未変性共役ジエン系ゴムは、共役ジエン及び必要に応じて共役ジエン以外の他の単量体を、例えば、乳化重合法、又は溶液重合法等により重合して得ることができる。
乳化剤としては、例えば炭素数10以上の長鎖脂肪酸塩及びロジン酸塩等が挙げられる。長鎖脂肪酸塩としては、例えば、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、ステアリン酸等の脂肪酸のカリウム塩又はナトリウム塩などが挙げられる。
分散溶媒としては通常、水が使用され、重合時の安定性が阻害されない範囲で、メタノール、エタノール等の水溶性有機溶媒を含んでいてもよい。
ラジカル重合開始剤としては、例えば過硫酸アンモニウムや過硫酸カリウムのような過硫酸塩、有機過酸化物、過酸化水素等が挙げられる。
得られる未変性共役ジエン系ゴムの分子量を調整するため、連鎖移動剤を使用してもよい。連鎖移動剤としては、例えば、t-ドデシルメルカプタン、n-ドデシルメルカプタン等のメルカプタン類;四塩化炭素、チオグリコール酸、ジテルペン、ターピノーレン、γ-テルピネン、α-メチルスチレンダイマーなどが挙げられる。
重合反応は、重合停止剤の添加により停止できる。重合停止剤としては、例えば、イソプロピルヒドロキシルアミン、ジエチルヒドロキシルアミン、ヒドロキシルアミン等のアミン化合物、ヒドロキノンやベンゾキノン等のキノン系化合物、亜硝酸ナトリウムなどが挙げられる。
重合反応停止後、必要に応じて老化防止剤を添加してもよい。重合反応停止後、得られたラテックスから必要に応じて未反応単量体を除去し、次いで、塩化ナトリウム、塩化カルシウム、塩化カリウム等の塩を凝固剤とし、必要に応じて硝酸、硫酸等の酸を添加して凝固系のpHを所定の値に調整しながら、重合化物を凝固させた後、分散溶媒を分離することによって重合化物を回収する。次いで水洗、及び脱水後、乾燥することで、未変性共役ジエン系ゴムが得られる。なお、凝固の際に、必要に応じて予めラテックスと乳化分散液にした伸展油とを混合し、油展した未変性共役ジエン系ゴムとして回収してもよい。
溶媒としては、例えば、n-ブタン、n-ペンタン、イソペンタン、n-ヘキサン、n-ヘプタン、イソオクタン等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂環式炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素などが挙げられる。
アニオン重合可能な活性金属としては、例えば、リチウム、ナトリウム、カリウム等のアルカリ金属;ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム等のアルカリ土類金属;ランタン、ネオジム等のランタノイド系希土類金属などが挙げられる。これらアニオン重合可能な活性金属の中でもアルカリ金属及びアルカリ土類金属が好ましく、アルカリ金属がより好ましい。
前記有機アルカリ金属化合物の使用量は、未変性共役ジエン系ゴム及び変性共役ジエン系ゴムの溶融粘度、分子量等に応じて適宜設定できるが、共役ジエンを含む全単量体100質量部に対して、通常0.01~3質量部の量で使用される。
前記有機アルカリ金属化合物は、ジブチルアミン、ジヘキシルアミン、ジベンジルアミン等の第2級アミンと反応させて、有機アルカリ金属アミドとして使用することもできる。
溶液重合の温度は、通常-80~150℃の範囲、好ましくは0~100℃の範囲、より好ましくは10~90℃の範囲である。重合様式は回分式あるいは連続式のいずれでもよい。
重合反応は、重合停止剤の添加により停止できる。重合停止剤としては、例えば、メタノール、イソプロパノール等のアルコールが挙げられる。得られた重合反応液をメタノール等の貧溶媒に注いで、重合化物を析出させるか、重合反応液を水で洗浄し、分離後、乾燥することにより未変性共役ジエン系ゴムを単離できる。
未変性共役ジエン系ゴムの製造方法としては、前記方法の中でも、溶液重合法が好ましい。
製造方法(1)で用いる変性化合物は、水素結合性官能基を有しているものであれば特に制限はない。水素結合性官能基としては、前述と同様のものが挙げられる。それらの中でも、水素結合力の強さという観点から、アミノ基、イミダゾール基、ウレア基、ヒドロキシ基、メルカプト基、シラノール基、アルデヒド基、カルボキシル基及びその誘導体が好ましい。カルボキシル基の誘導体としては、その塩、そのアミド化体、又はその酸無水物が好ましい。これらの水素結合性官能基を有する変性化合物は、1種単独で用いてもよく、2種以上を併用してもよい。
また、未変性共役ジエン系ゴムに前記変性化合物をグラフト化し水素結合性官能基を導入した後、さらに該官能基と反応し得る変性化合物を添加して別の水素結合性官能基を重合体中に導入してもよい。具体的には、例えば、リビングアニオン重合して得られる未変性共役ジエン系ゴムに対し、無水マレイン酸をグラフト化した後、次いで2-ヒドロキシエチルメタクリレートやメタノール、水等の化合物を反応させる方法が挙げられる。
前記方法で使用される有機溶媒としては、一般的には炭化水素系溶媒、ハロゲン化炭化水素系溶媒が挙げられる。これら有機溶媒の中でも、n-ブタン、n-ヘキサン、n-ヘプタン、シクロヘキサン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒が好ましい。
老化防止剤の添加量は、未変性共役ジエン系ゴム100質量部に対して、0.01~10質量部が好ましく、0.05~5質量部がより好ましい。
製造方法(2)としては、共役ジエン単量体と水素結合性官能基を有するラジカル重合性化合物とを、公知の方法でランダム共重合、ブロック共重合又はグラフト共重合する方法が挙げられる。
製造方法(2)で用いる水素結合性官能基を有するラジカル重合性化合物は、分子内に水素結合性官能基と反応性多重結合を有する化合物であれば特に制限なく用いることができる。具体的には、反応性の多重結合を有するアルデヒド、該アルデヒドのアセタール化体;反応性の多重結合を有するモノカルボン酸、該モノカルボン酸の塩、該モノカルボン酸のエステル化体、該モノカルボン酸の酸無水物;反応性の多重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、該ジカルボン酸の酸無水物;及び反応性の多重結合を有するアミン化合物等が挙げられる。
なお、本明細書において、前記「(メタ)アクリル酸」は、「アクリル酸」と「メタクリル酸」との総称を意味する。
製造方法(3)は、重合活性末端を有する未変性の共役ジエン単量体の重合化物(未変性共役ジエン系ゴム)に対して、重合停止剤を添加する前に該重合活性末端と反応し得る変性化合物を添加する方法である。重合活性末端を有する未変性共役ジエン系ゴムは、前記製造方法(1)と同様に、例えば、乳化重合法、又は溶液重合法等により共役ジエン単量体及び必要に応じて共役ジエン以外の他の単量体を重合して得ることができる。
製造方法(3)において用いることができる変性化合物としては、例えば、ジメチルジエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、3-アミノプロピルトリエトキシシラン、テトラグリシジル-1,3-ビスアミノメチルシクロヘキサン、2,4-トリレンジイソシアネート、二酸化炭素、酸化エチレン、無水コハク酸、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、N-ビニルピロリドン、N-メチルピロリドン、4-ジメチルアミノベンジリデンアニリン、ジメチルイミダゾリジノン等の変性剤、又は特開2011-132298号公報に記載のその他の変性剤が挙げられる。
前記変性化合物の使用量は、例えば有機アルカリ金属化合物を用いて重合する場合、該有機アルカリ金属化合物に対して、好ましくは0.01~100モル等量の範囲である。反応温度は通常-80~150℃であり、好ましくは0~100℃、より好ましくは10~90℃の範囲である。
また、重合停止剤を添加する前に前記変性化合物を添加し未変性共役ジエン系ゴムに水素結合性官能基を導入した後、さらに該官能基と反応し得る変性化合物を添加して別の水素結合性官能基を重合体中に導入してもよい。
前記エチレン性不飽和単量体としては、例えば、エチレン、1-ブテン、及びイソブチレン等のオレフィンなどが挙げられる。
前記芳香族ビニル化合物としては、例えば、スチレン、α-メチルスチレン、2-メチルスチレン、3-メチルスチレン、4-メチルスチレン、4-プロピルスチレン、4-t-ブチルスチレン、4-シクロヘキシルスチレン、4-ドデシルスチレン、2,4-ジメチルスチレン、2,4-ジイソプロピルスチレン、2,4,6-トリメチルスチレン、2-エチル-4-ベンジルスチレン、4-(フェニルブチル)スチレン、1-ビニルナフタレン、2-ビニルナフタレン、ビニルアントラセン、N,N-ジエチル-4-アミノエチルスチレン、ビニルピリジン、4-メトキシスチレン、モノクロロスチレン、ジクロロスチレン、及びジビニルベンゼン等が挙げられる。これらは、1種単独で用いてもよく、2種以上を併用してもよい。
変性共役ジエン系ゴムが前記エチレン性不飽和単量体又は/及び前記芳香族ビニル化合物に由来する単量体単位を含有する場合、その含有量は30モル%以下が好ましく、10モル%以下がより好ましく、5モル%以下が更に好ましい。
変性共役ジエン系ゴムの重量平均分子量(Mw)は特に制限されないが、取り扱い性の観点から、200,000以下が好ましく、120,000以下がより好ましく、100,000以下が更に好ましく、75,000以下がより更に好ましく、50,000以下が特に好ましく、そして、接着性を向上させる観点から、10,000超が好ましく、20,000以上がより好ましく、22,000以上が更に好ましく、25,000以上がより更に好ましい。
変性共役ジエン系ゴムの数量平均分子量(Mn)は特に制限されないが、取り扱い性の観点から、200,000以下が好ましく、120,000以下がより好ましく、100,000以下が更に好ましく、75,000以下がより更に好ましく、50,000以下が特に好ましく、そして、接着性を向上させる観点から、10,000超が好ましく、20,000以上がより好ましく、22,000以上が更に好ましく、25,000以上がより更に好ましい。
変性共役ジエン系ゴムのMw及びMnは、ゲルパーミエーションクロマトグラフィー(GPC)の測定から求めたポリスチレン換算の重量平均分子量及び数平均分子量である。
変性共役ジエン系ゴムの分子量分布(Mw/Mn)は、1.0~5.0が好ましく、1.0~3.0がより好ましく、1.0~2.0が更に好ましく、1.0~1.5がより更に好ましく、1.0~1.3が特に好ましい。Mw/Mnが前記範囲内であると、変性共役ジエン系ゴムの粘度のばらつきが小さく、取り扱いが容易である。分子量分布(Mw/Mn)は、GPCの測定により求めた標準ポリスチレン換算の重量平均分子量(Mw)/数平均分子量(Mn)の比を意味する。
本明細書において「液状」とは、変性共役ジエン系ゴムの38℃で測定した溶融粘度が0.1~4,000Pa・sであることを示す。該溶融粘度は1~2,000Pa・sがより好ましく、1~1,000Pa・sが更に好ましい。なお、変性共役ジエン系ゴムの溶融粘度は、38℃においてブルックフィールド型粘度計により測定した値である。
変性共役ジエン系ゴムのビニル含量は99モル%以下であることが好ましく、90モル%以下であることがより好ましい。本明細書において「ビニル含量」とは、変性液状ジエン系ゴムに含まれる、共役ジエン単位の合計100モル%中、1,2-結合又は3,4-結合で結合をしている共役ジエン単位(1,4-結合以外で結合をしている共役ジエン単位)の合計モル%を意味する。ビニル含量は、1H-NMRを用いて1,2-結合又は3,4-結合で結合をしている共役ジエン単位由来のシグナルと1,4-結合で結合をしている共役ジエン単位由来のシグナルの積分値比から算出することができる。
また、前記接着成分は、ゴムとの接着力を阻害しない範囲内で、変性共役ジエン系ゴム以外の他の成分を含んでもよい。
前記他の成分としては、他のポリマー(例えば未変性共役ジエン系ゴム)、酸、アルカリ、酸化防止剤、硬化剤、分散剤、顔料、染料、接着助剤、カーボンブラック、油剤等が挙げられる。これらの中でも、接着成分の粘度を低下させ、取り扱い性を向上させる観点から、未変性共役ジエン系ゴムや鉱物油等を主成分とした油剤を変性共役ジエン系ゴムと併用することが好ましい。
前記他の成分の含有量は、例えば未変性共役ジエン系ゴム及び/又は油剤を含む場合、変性共役ジエン系ゴム100質量部に対して、好ましくは1~10,000質量部、より好ましくは30~5,000質量部、更に好ましくは50~1,000質量部である。
また、前記接着成分中の変性共役ジエン系ゴムの含有量は、ゴムとの接着力を向上させる観点から、好ましくは10質量%以上、より好ましくは30質量%以上、更に好ましくは50質量%以上であり、そして、好ましくは100質量%以下である。
本発明の補強繊維は、親水性繊維及び接着成分を含有する補強繊維であって、該親水性繊維の表面の少なくとも一部に該接着成分を有するものである。本発明に用いることができる親水性繊維としては、合成繊維、天然繊維、及び再生繊維等を挙げることができる。親水性繊維は、1種単独で用いてもよく、2種以上を併用してもよい。
このような熱可塑性樹脂の具体例は、ポリビニルアルコール系樹脂、ポリアミド系樹脂〔ポリアミド6、ポリアミド66、ポリアミド11、ポリアミド12、ポリアミド610、ポリアミド612、ポリアミド9C(ノナンジアミンとシクロヘキサンジカルボン酸からなるポリアミド)等の脂肪族ポリアミド;ポリアミド9T(ノナンジアミンとテレフタル酸からなるポリアミド)等の芳香族ジカルボン酸と脂肪族ジアミンとから合成される半芳香族ポリアミド;ポリパラフェニレンテレフタルアミド等の芳香族ジカルボン酸と芳香族ジアミンとから合成される全芳香族ポリアミド等〕、ポリアクリルアミド系樹脂等が挙げられる。
これらの中でも、ポリビニルアルコール系樹脂、及びポリアミド系樹脂が好ましい。親水性の合成繊維は、1種単独で用いてもよく、2種以上を併用してもよい。また、これらの親水性の合成繊維は、親水性をより高めるべく、後述する親水化処理を更に施してもよい。
親水性の再生繊維としては、レーヨン、リヨセル、キュプラ、及びポリノジック等の再生セルロース繊維が挙げられる。
これらの天然繊維及び再生繊維は、それぞれ1種単独で用いてもよく、2種以上を併用してもよい。また、これらの親水性の天然繊維及び再生繊維は、親水性をより高めるべく、後述する親水化処理を更に施してもよい。
本発明においては、親水性繊維を用いることにより接着成分に含まれる変性共役ジエン系ゴムと親水性繊維とが強い親和効果を発現し、接着成分と該親水性繊維が強固に結びつくことから、ゴムに対する接着力をより優れたものとすることができる。
なお、ポリビニルアルコール系繊維としては、本発明の補強繊維を自動車用ホース、特に自動車用ブレーキオイルホースに好適に用いる観点から、株式会社クラレから商品名「ビニロン」として市販されており、単糸繊度が0.1~30dtex程度のものを好適に用いることができる。
本発明の補強繊維の製造方法は、親水性繊維の表面の少なくとも一部に前記接着成分を付着又は含有させる方法であれば特に制限はない。
親水性繊維に前記接着成分を付着させる際には、該接着成分の他に溶媒として、水、エタノール、プロパノール、ブタノール、メタノール、トルエン、キシレン、アセトン、ヘキサン、テトラヒドロフラン、メチルエチルケトン、ジオキサン、テトラヒドロフラン、及び酢酸エチル等を用いてもよい。溶媒を用いる場合、その使用量は、接着成分と溶媒との合計中、好ましくは10~99.9質量%、より好ましくは40~99.9質量%、更に好ましくは70~99.0質量%である。
方法(I)としては、親水性繊維の表面に前記接着成分からなる接着層を形成する方法であれば特に制限はないが、ゴムとの接着性を向上させる観点から、下記工程I-1を含む方法が好ましい。
工程I-1:前記接着成分を親水性繊維の表面に付着させる工程
前記接着成分を付着させる方法として、浸漬、ロールコーター、ノズル(スプレー)塗布、及び刷毛塗り等から選ばれる1種以上により行うことが好ましい。
水中油滴型エマルションや溶媒に溶かして付着させる場合には、水又は溶媒を風乾等の乾燥処理により揮発させることが好ましい。
機械的方法としてはホモジナイザー、ホモミキサー、ディスパーサーミキサー、コロイドミル、パイプラインミキサー、高圧ホモジナイザー、超音波乳化機等が挙げられ、これらを単独又は組み合わせて使用できる。
化学的方法としては、反転乳化法、D相乳化法、HLB温度乳化法、ゲル乳化法及び液晶乳化法等種々の方法が挙げられ、簡便に粒子径の細かいエマルションが得られる観点から反転乳化法が好ましい。また粒子径の細かいエマルションを得るためには、変性共役ジエン系ゴムの粘度を下げる目的で適当な温度(例えば30~80℃)で加熱しながら前記作業を実施することが好ましい場合もある。エマルション調製の際はエマルションの安定性向上の観点から、固形分濃度20~80質量%で調製することが好ましく、30~70質量%がより好ましい。
乳化剤としてはオレイン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等のカリウム又はナトリウム塩等の脂肪酸石鹸、ロジン、不均化ロジン等のカリウム又はナトリウム塩等の樹脂石鹸、アルキルベンゼンスルホン酸やアルキルナフタレンスルホン酸等のナトリウム又はカリウム塩等のスルホン酸石鹸、オレイル硫酸エステル、ラウリル硫酸エステル、ポリオキシエチレンアルキル硫酸エステル等のナトリウム塩等の硫酸エステル石鹸、ヘキサデシルフォスフェート、ポリオキシエチレンラウリルエーテルフォスフェート、ポリオキシエチレントリデシルエーテルフォスフェート、ポリオキシエチレンノニルフェニルフォスフェート等のリン酸塩石鹸等のアニオン石鹸、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールラウレート、ポリエチレングリコールオレエート等のノニオン石鹸、ドデシルアミン塩酸塩等の脂肪族アミン塩酸塩、オクチルトリメチルアンモニウムクロライド、ジオクチルジメチルアンモニウムクロライド、ベンジルジメチルオクチルアンモウニウム塩、ドデシルピリジウムクロライド等のアルキルピリジウム塩等のカチオン石鹸などが挙げられる。これらは単独でも混合して用いてもよい。
工程I-2:工程I-1で得られた前記接着成分が付着した親水性繊維を熱処理する工程
工程I-2における熱処理は、好ましくは100~200℃の処理温度で0.1秒~2分の処理時間で行うことが好ましい。前記接着成分に含まれる変性共役ジエン系ゴムは反応性多重結合を有しているため、酸素存在下での熱処理は200℃以下であることが好ましく、175℃以下であることがより好ましい。熱処理の温度が前記範囲内であると、変性共役ジエン系ゴム中の反応性多重結合量が減少することなく、接着力を向上させることができ、更に繊維の劣化も抑制し、着色等の品質も良好となる。
本発明の補強繊維の製造方法は、前記接着成分を原料の一部として含有する繊維として製造する方法(II)であってもよい。
前記補強繊維が前記接着成分を原料の一部として含有する場合の接着成分以外の原料について特に制限はないが、例えば、ポリビニルアルコール、ポリエステル、ナイロン、トリアセテート、ジアセテート、ポリアミド、及びこれらの混合物が挙げられ、中でも、接着成分との混合のし易さ、及び補強繊維の強度の観点から、ポリビニルアルコールが好ましい。
前記補強繊維中の前記親水性繊維及び前記接着成分の合計含有量は、ゴムとの接着力の向上及び補強強度の観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上である。
前記補強繊維は、単糸繊度が0.1dtex以上30dtex以下のマルチフィラメントであることが好ましい。単糸繊度は0.1dtex未満であってもよいが工業的に製造することが難しいことから0.1dtex以上が好ましい。また、単糸繊度が30dtex以下であると、補強繊維とした場合における繊維の表面積が大きくなるため、ゴムとの接着性が向上する。当該観点から、本発明の補強繊維は、単糸繊度がより好ましくは0.3dtex以上、更に好ましくは0.5dtex以上、より更に好ましくは1dtex以上であり、そして、より好ましくは20dtex以下、更に好ましくは15dtex以下、より更に好ましくは10dtex以下であるマルチフィラメントであることが好ましい。
本発明の成形体は、前記補強繊維を用いたものであれば特に限定されない。中でも、前記補強繊維がゴムとの優れた接着性を有することから、特に前記補強繊維とゴム成分とを用いた成形体(以下、「ゴム成形体」とも称する)が好ましい。前記ゴム成形体に用いられる補強繊維は、ゴムの形態保持という観点からは、該補強繊維を少なくとも一部に含む織物又は編物として用いられることが好ましく、該補強繊維を少なくとも一部に含む織物又は編物からなる補強層とゴム層とを積層した積層体として用いられることがより好ましい。
前記自動車用タイヤとしては、例えばベルト、カーカス プライ、ブレーカー、ビードテープ等の補強繊維とゴム成分との複合材からなる各種部材に使用できる。
前記ホースとしては、種々の用途における各種流体の輸送を目的に使用することができ、例えば、自動車用の流体輸送用ホースに好適であり、特に、自動車用の液体燃料用ホース、自動車用のブレーキオイルホース、及び冷媒用ホースに用いることが好ましく、自動車用のブレーキオイルホースに用いることがより好ましい。
ゴム成分としては、特に限定はされないが、例えば、NR(天然ゴム)、IR(ポリイソプレンゴム)、BR(ポリブタジエンゴム)、SBR(スチレン-ブタジエンゴム)、NBR(ニトリルゴム)、EPM(エチレン-プロピレン共重合体ゴム)、EPDM(エチレン-プロピレン-非共役ジエン共重合体ゴム)、IIR(ブチルゴム)、ハロゲン化ブチルゴム、CR(クロロプレンゴム)等が挙げられる。これらの中でも、NR、IR、BR、SBR、EPDM、CRを用いることが好ましく、EPDMを用いることがより好ましい。これらのゴム成分は1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。タイヤ用途においては、タイヤ工業において一般的に用いられるものが使用できる。中でも、天然ゴム単独、あるいは天然ゴムとSBRとを組み合わせて使用することが好ましい。天然ゴムとSBRとを組み合わせる際は、ゴムの加硫戻りによる物性低下を抑制する観点から、天然ゴムとSBRとの質量比(天然ゴム/SBR)は、50/50~90/10の範囲とすることが好ましい。
前記SBRの重量平均分子量(Mw)は100,000~2,500,000であることが好ましく、150,000~2,000,000であることがより好ましく、200,000~1,500,000であることが更に好ましい。前記範囲である場合、加工性と機械強度を両立することができる。なお、SBRの重量平均分子量とは、ゲルパーミエーションクロマトグラフィー(GPC)の測定から求めたポリスチレン換算の重量平均分子量である。
前記SBRとしては、本発明の効果を損ねない範囲であれば、SBRに官能基が導入された変性SBRを用いてもよい。官能基としては、例えばアミノ基、アルコキシシリル基、ヒドロキシ基、エポキシ基、カルボキシル基等が挙げられる。
機械強度の向上等の物性の改善などの観点からは、前記フィラーの中でも、カーボンブラック及びシリカが好ましい。
前記カーボンブラックの平均粒径としては、5~100nmが好ましく、5~80nmがより好ましく、5~70nmが更に好ましい。なお、前記カーボンブラックの平均粒径は、透過型電子顕微鏡により粒子の直径を測定してその平均値を算出することにより求めることができる。
前記シリカの平均粒径は、0.5~200nmが好ましく、5~150nmがより好ましく、10~100nmが更に好ましい。
なお、前記シリカの平均粒径は、透過型電子顕微鏡により粒子の直径を測定して、その平均値を算出することにより求めることができる。
また、前記フィラーとして、シリカ及びカーボンブラック以外のフィラーを用いる場合には、その含有量は、前記ゴム成分100質量部に対して、20~120質量部が好ましく、20~90質量部がより好ましく、20~80質量部が更に好ましい。
これらフィラーは1種単独で用いてもよく、2種以上を併用してもよい。
これらシランカップリング剤は、1種単独で用いてもよく、2種以上を併用してもよい。前記シランカップリング剤は、シリカ100質量部に対して好ましくは0.1~30質量部、より好ましくは0.5~20質量部、更に好ましくは1~15質量部含有される。シランカップリング剤の含有量が前記範囲内であると、分散性、カップリング効果、補強性が向上する。
内側ゴム層と外側ゴム層を構成するゴム成分としては、前述のものが挙げられる。中でも、内側ゴム層を構成するゴム成分としては、EPDM、SBR等が挙げられ、外側ゴム層を構成するゴム成分としては、EPDM、CR等が挙げられる。前記補強層は、補強繊維を編組して形成することができる。
前記ブレーキオイルホースの製造方法としては、内側ゴム層の外表面上に、前記補強繊維を編組した補強層(第1補強層)を形成する。2層の補強層を形成する場合には、第1補強層の外表面上に更に中間ゴム層を形成し、該中間ゴム層の外表面上に、前記補強繊維を編組した補強層(第2補強層)を形成してもよい。そして、補強層(第1補強層又は第2補強層)の外表面上に外側ゴム層を形成し、加硫することにより製造することができる。
加硫温度は、ブレーキオイルホースの各層の構成材料の種類等により適宜選択できるが、ゴムと補強繊維の劣化を抑制し、ゴムと補強繊維との接着力を向上させる観点から、200℃以下であることが好ましい。
<変性共役ジエン系ゴムの製造>
・下記式(1a)で表される単量体単位を有する変性共役ジエン系ゴムの製造
十分に乾燥した5Lオートクレーブを窒素置換し、ヘキサン1200g及びn-ブチルリチウム(17質量%ヘキサン溶液)26.2gを仕込み、50℃に昇温した後、撹拌条件下、重合温度を50℃となるように制御しながら、イソプレン1200gを逐次添加して、1時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を70℃で24時間真空乾燥することにより、未変性液状ポリイソプレン(A’-1)を得た。
続いて、窒素置換を行った容量1Lのオートクレーブ中に、得られた未変性液状ポリイソプレン(A’-1)500gを仕込み、無水マレイン酸25gとブチル化ヒドロキシトルエン(BHT)0.5gを添加し、170℃で15時間反応させて、無水マレイン酸変性液状ポリイソプレン(A-1)を得た。
窒素置換を行った容量1Lのオートクレーブ中に、製造例1と同様の手順で得られた未変性液状ポリイソプレン(A’-1)500gを仕込み、無水マレイン酸7.5gとブチル化ヒドロキシトルエン(BHT)0.5gを添加し、170℃で15時間反応させて、無水マレイン酸変性液状ポリイソプレン(A-2)を得た。
窒素置換を行った容量1Lのオートクレーブ中に、製造例1と同様の手順で得られた未変性液状ポリイソプレン(A’-1)500gを仕込み、無水マレイン酸50gとブチル化ヒドロキシトルエン(BHT)0.5gを添加し、170℃で15時間反応させて、無水マレイン酸変性液状ポリイソプレン(A-3)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、ヘキサン1260g及びn-ブチルリチウム(17質量%ヘキサン溶液)36.3gを仕込み、50℃に昇温した後、撹拌条件下、重合温度を50℃となるように制御しながら、ブタジエン1260gを逐次添加して、1時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を70℃で24時間真空乾燥することにより、未変性液状ポリブタジエン(A’-2)を得た。
続いて、窒素置換を行った容量1Lのオートクレーブ中に、得られた未変性液状ポリブタジエン(A’-2)500gを仕込み、無水マレイン酸25gとN-フェニル-N'-(1,3-ジメチルブチル)-p-フェニレンジアミン(商品名「ノクラック6C」、大内新興化学工業株式会社製)0.5gを添加し、170℃で24時間反応させて、無水マレイン酸変性液状ポリブタジエン(A-4)を得た。
窒素置換を行った容量1Lのオートクレーブ中に、製造例3と同様の手順で得られた未変性液状ポリブタジエン(A’-2)500gを仕込み、3-メルカプトプロピルトリエトキシシラン37gとブチル化ヒドロキシトルエン(BHT)0.5gを添加し、105℃で8時間反応させて、トリエトキシシラン変性液状ポリブタジエン(A-5)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、ヘキサン1200g及びn-ブチルリチウム(17質量%ヘキサン溶液)5.0gを仕込み、50℃に昇温した後、撹拌条件下、重合温度を50℃となるように制御しながら、β-ファルネセン1200gを逐次添加して、1時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を70℃で24時間真空乾燥することにより、未変性液状ポリファルネセン(A’-3)を得た。
続いて、窒素置換を行った容量1Lのオートクレーブ中に、得られた未変性液状ポリファルネセン(A’-3)500gを仕込み、無水マレイン酸25gとブチル化ヒドロキシトルエン(BHT)0.5gを添加し、170℃で24時間反応させて、無水マレイン酸変性液状ポリファルネセン(A-6)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、ヘキサン1200g及びsec-ブチルリチウム(10.5質量%シクロヘキサン溶液)32.8gを仕込み、50℃に昇温した後、撹拌条件下、重合温度を50℃となるように制御しながら、予め調製したβ-ファルネセンとブタジエンの混合物(β-ファルネセン858gとブタジエン572gをボンベ内で混合)1430gを12.5ml/分で加えて1時間重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を70℃で24時間真空乾燥することにより、未変性液状ファルネセン-ブタジエンランダム共重合体(A’-4)を得た。
続いて、窒素置換を行った容量1Lのオートクレーブ中に、得られた未変性液状ファルネセン-ブタジエンランダム共重合体(A’-4)500gを仕込み、無水マレイン酸25gとブチル化ヒドロキシトルエン(BHT)0.5gを添加し、170℃で24時間反応させて、無水マレイン酸変性液状ファルネセン-ブタジエンランダム共重合体(A-7)を得た。
(重量平均分子量、数平均分子量及び分子量分布の測定方法)
変性共役ジエン系ゴムのMw、Mn及びMw/Mnは、GPC(ゲルパーミエーションクロマトグラフィー)により標準ポリスチレン換算値として求めた。測定装置及び条件は、以下の通りである。
・装置 :東ソー株式会社製GPC装置「GPC8020」
・分離カラム :東ソー株式会社製「TSKgelG4000HXL」
・検出器 :東ソー株式会社製「RI-8020」
・溶離液 :テトラヒドロフラン
・溶離液流量 :1.0ml/分
・サンプル濃度:5mg/10ml
・カラム温度 :40℃
変性共役ジエン系ゴムの38℃における溶融粘度をブルックフィールド型粘度計(BROOKFIELD ENGINEERING LABS. INC.製)により測定した。
変性共役ジエン系ゴム1分子当たりの平均水素結合性官能基数は、変性共役ジエン系ゴムの水素結合性官能基の当量(g/eq)とスチレン換算の数平均分子量Mnから、下記式より算出した。
1分子当たりの平均水素結合性官能基数=[(数平均分子量(Mn))/(スチレン単位の分子量)×(共役ジエン及び必要に応じて含まれる共役ジエン以外の他の単量体単位の平均分子量)]/(水素結合性官能基の当量)
なお、水素結合性官能基の当量の算出方法は、水素結合性官能基の種類により適宜選択することができる。
変性反応後の試料をメタノールで4回洗浄(試料1gに対して5mL)して酸化防止剤等の不純物を除去した後、試料を80℃で12時間、減圧乾燥した。変性反応後の試料3gにトルエン180mL、エタノール20mLを加え溶解した後、0.1N水酸化カリウムのエタノール溶液で中和滴定し、下記式より酸価を求めた。
酸価(mgKOH/g)=(A-B)×F×5.611/S
A:中和に要した0.1N水酸化カリウムのエタノール溶液滴下量(mL)
B:試料を含まないブランクでの0.1N水酸化カリウムのエタノール溶液滴下量(mL)
F:0.1N水酸化カリウムのエタノール溶液の力価
S:秤量した試料の質量(g)
〔1g当たり水素結合性官能基質量〕=〔酸価〕/〔56.11〕×〔水素結合性官能基分子量〕/1000
〔1g当たり重合体主鎖質量〕=1-〔1g当たり水素結合性官能基質量〕
〔水素結合性官能基の当量〕=〔1g当たり重合体主鎖質量〕/(〔1g当たり水素結合性官能基質量〕/〔水素結合性官能基分子量〕)
未変性共役ジエン系ゴム100質量部に対して付加された変性化合物量(質量部)を、下記式に基づき算出した。
〔付加された変性化合物量〕=〔1g当たり水素結合性官能基質量〕/〔1g当たりの重合体主鎖質量〕×100
調製例1:変性共役ジエン系ゴム(A-1)のエマルション(E-1)の調製
変性共役ジエン系ゴム(A-1)250gに乳化剤(ポリオキシエチレンアルキル(C=12~15)エーテルフォスフェート)(商品名「フォスファノールRS-710」、東邦化学工業株式会社製)15gを加えて20分間撹拌した。続いて撹拌しながら0.7mol/L水酸化ナトリウム水溶液180gを少しずつ添加した。所定量の水を添加後、20分撹拌することで、変性共役ジエン系ゴム(A-1)のエマルション(E-1)を得た。
変性共役ジエン系ゴム(A-2)250gに乳化剤(ポリオキシエチレンアルキル(C=12~15)エーテルフォスフェート)(商品名「フォスファノールRS-710」、東邦化学工業株式会社製)15gを加えて20分間撹拌した。続いて撹拌しながら0.7mol/L水酸化ナトリウム水溶液56gを少しずつ添加し、さらに少しずつ水124gを添加した。所定量の水を添加後、20分撹拌することで、変性共役ジエン系ゴム(A-2)のエマルション(E-2)を得た。
変性共役ジエン系ゴム(A-3)250gに乳化剤(ポリオキシエチレンアルキル(C=12~15)エーテルフォスフェート)(商品名「フォスファノールRS-710」、東邦化学工業株式会社製)15gを加えて20分間撹拌した。続いて撹拌しながら1.4mol/L水酸化ナトリウム水溶液180gを少しずつ添加した。所定量の水を添加後、20分撹拌することで、変性共役ジエン系ゴム(A-3)のエマルション(E-3)を得た。
変性共役ジエン系ゴム(A-4)250gに乳化剤(ポリオキシエチレンアルキル(C=12~15)エーテルフォスフェート)(商品名「フォスファノールRS-710」、東邦化学工業株式会社製)15gを加えて20分間撹拌した。続いて撹拌しながら0.7mol/L水酸化ナトリウム水溶液180gを少しずつ添加した。所定量の水を添加後、20分撹拌することで、変性共役ジエン系ゴム(A-4)のエマルション(E-4)を得た。
変性共役ジエン系ゴム(A-5)250gに乳化剤(ポリオキシエチレンアルキル(C=12~15)エーテルフォスフェート)(商品名「フォスファノールRS-710」、東邦化学工業株式会社製)15gを加えて20分間撹拌した。続いて撹拌しながら1mol/L水酸化ナトリウム水溶液21gを少しずつ添加し、さらに少しずつ水159gを添加した。所定量の水を添加後、20分撹拌することで、変性共役ジエン系ゴム(A-5)のエマルション(E-5)を得た。
変性共役ジエン系ゴム(A-6)250gに乳化剤(ポリオキシエチレンアルキル(C=12~15)エーテルフォスフェート)(商品名「フォスファノールRS-710」、東邦化学工業株式会社製)15gを加えて20分間撹拌した。続いて撹拌しながら0.7mol/L水酸化ナトリウム水溶液180gを少しずつ添加した。所定量の水を添加後、20分撹拌することで、変性共役ジエン系ゴム(A-6)のエマルション(E-6)を得た。
変性共役ジエン系ゴム(A-7)250gに乳化剤(ポリオキシエチレンアルキル(C=12~15)エーテルフォスフェート)(商品名「フォスファノールRS-710」、東邦化学工業株式会社製)15gを加えて20分間撹拌した。続いて撹拌しながら0.7mol/L水酸化ナトリウム水溶液180gを少しずつ添加した。所定量の水を添加後、20分撹拌することで、変性共役ジエン系ゴム(A-7)のエマルション(E-7)を得た。
接着成分の付着量は、以下の測定方法により測定した。
補強繊維約10gを試料として採取し、その質量Xを測定した。試料から接着成分を抽出し、抽出質量Yを測定した。抽出には溶媒にトルエンを用い、ソックスレー抽出器で3時間抽出を行った。接着成分の付着量を下記式により算出した。
補強繊維に対する接着成分の付着量(質量%)=(Y/X)×100
また、接着成分中の変性共役ジエン系ゴム含有量(質量%)は、接着成分における固形分中の変性共役ジエン系ゴムの質量比から算出した。
実施例1として、親水性繊維の表面の少なくとも一部に接着成分からなる接着層を有する補強繊維を製造し、以下のとおり評価した。
前述のとおり製造した変性共役ジエン系ゴム(A-1)からなる接着成分を、固形分濃度が4質量%となるようにテトラヒドロフランに溶解させた。この溶液中に親水性繊維としてポリビニルアルコール系繊維であるビニロン繊維(株式会社クラレ製「クラロン1239」、総繊度1330dtex、単糸繊度6.65dtex)を浸漬した後、引き上げてドラフト内で風乾させた。このようにして接着成分を付着させたビニロンを撚り数80T/mで撚って繊維コードを作製した。
実施例2~8として、親水性繊維の表面の少なくとも一部に接着成分からなる接着層を有する補強繊維を製造し、以下のとおり評価した。
前述のとおり製造した変性共役ジエン系ゴムのエマルション(E-1)~(E-7)からなる接着成分を、固形分濃度が4質量%となるように、それぞれ水に分散させた。この分散液に対してビニロン繊維(株式会社クラレ製「クラロン1239」、総繊度1330dtex、単糸繊度6.65dtex)を浸漬した後、ローラーで搾液した。次いで、得られた繊維を120℃で30秒間乾燥処理し、170℃で30秒間熱処理した。このようにして接着成分を付着させたビニロンを撚り数80T/mで撚って繊維コードを作製した。
比較例1は、接着成分として未変性共役ジエン系ゴム(A’-1)を用いたこと以外は実施例1と同様の方法で繊維コードを作製した。
比較例2は、ビニロン繊維の代わりに疎水性のポリエステル系繊維であるPET繊維(東レ株式会社製「702C」、総繊度1670dtex、単糸繊度5.80dtex)、を用いたこと以外は実施例2と同様の方法で繊維コードを作製した。
参考例1は、ビニロン繊維(株式会社クラレ製「クラロン1239」、総繊度1330dtex、単糸繊度6.65dtex)に、付着量3.0質量%となるように公知のRFL処理を施した。このようにして接着成分を付着させたビニロンを撚り数80T/mで撚って繊維コードを作製した。なお、使用したRFL液は下記の方法にて調製した。
A液 水 :300質量部
レゾルシン : 22質量部
ホルムアルデヒド(有効分37質量%) : 33質量部
水酸化ナトリウム水溶液(有効分10質量%) : 7質量部
上記A液を25℃の温度で6時間熟成した。
ビニルピリジン変性SBRラテックス(有効分40質量%):244質量部
上記B液を熟成済みのA液と混合した後、25℃の温度で16時間熟成してRFL液を製造した。なお、繊維への付着量を調整するために上記操作後に水で2倍に希釈した。
前述の実施例、比較例及び参考例で作製した繊維コードを、繊維コード同士が重ならないようにスダレ状にマスキングテープ上に並べて固定した後、これと、別途EPDMゴム(住友化学株式会社製「エスプレン501A」)を用い、下記配合組成により調製したEPDMゴムを主成分とする未加硫のゴム組成物(以下、「EPDM未加硫ゴム」とも称する)(幅25.4mm、長さ240mm)とを重ね合わせた(繊維コードとEPDM未加硫ゴムとの重ね合わせた部分の長さは190mmであった)。次いで、150℃、圧力20kg/cm2の条件で30分間プレス加硫することにより評価用シートを作製した。
EPDMゴム :100質量部
フィラー(カーボンブラック) : 60質量部
軟化剤(パラフィン系プロセスオイル) : 20質量部
架橋剤(硫黄粉) :1.5質量部
加硫助剤(亜鉛華2種、ステアリン酸) : 6質量部
加硫促進剤(チアゾール系、チウラム系) :1.5質量部
得られた評価用シートについて、繊維コードをゴムからT型剥離させるときに要した力(N/25.4mm)を測定し、ゴム接着力として評価した。結果を表2に示す。ゴム接着力の評価結果は、数値が大きいほど補強繊維とゴムとの接着力が大きいことを示す。
得られた評価用シートの初期引張抵抗度を測定機(インストロン3365)を使用してJIS L 1013:2010に従って測定した。剥離速度50mm/minで200mm動かして剥離試験を行い、繊維コードとゴムとを剥離した。
チャートに現れる最初のピークから10mmと最後のピークから10mmを除いた範囲で現れる多数のピークから最高点5点と最低点5点を取り出して平均した値を繊維とゴムの初期引張抵抗度とした。なお、ピーク同士が2mm以上離れているもののみから値を採取した。結果を表2に示す。初期引張抵抗度の評価結果は、数値が大きいほど補強繊維とゴムとを接着した際の補強強度が高いことを示す。
実施例9は、親水性繊維としてビニロン繊維の代わりに、再生セルロース系繊維であるレーヨン繊維(Cordenka製「Cordenka700」、総繊度1840dtex、単糸繊度1.84dtex)を用いたこと以外は実施例1と同様の方法で繊維コードを作製した。
実施例10は、親水性繊維として後述の親水化処理を行ったポリエステル系繊維であるPET繊維(東レ株式会社製「702C」、総繊度1670dtex、単糸繊度5.80dtex)を用いたこと以外は実施例1と同様の方法で繊維コードを作製した。
比較例3は、親水性繊維としてビニロン繊維の代わりに、再生セルロース系繊維であるレーヨン繊維(Cordenka製「Cordenka700」、総繊度1840dtex、単糸繊度1.84dtex)を用いたこと以外は比較例1と同様の方法で繊維コードを作製した。
比較例4は、親水性繊維として後述の親水化処理を行ったポリエステル系繊維であるPET繊維(東レ株式会社製「702C」、総繊度1670dtex、単糸繊度5.80dtex)を用いたこと以外は比較例1と同様の方法で繊維コードを作製した。
参考例2は、親水性繊維としてビニロン繊維の代わりに、再生セルロース系繊維であるレーヨン繊維(Cordenka製「Cordenka700」、1840dtex)を用いたこと以外は参考例1と同様の方法で繊維コードを作製した。
参考例3は、親水性繊維として後述の親水化処理を行ったポリエステル系繊維であるPET繊維(東レ株式会社製「702C」、総繊度1670dtex、単糸繊度5.80dtex)を用いたこと以外は参考例1と同様の方法で繊維コードを作製した。
下記の組成に調整した水溶液中にポリエステル系繊維であるPET繊維(東レ株式会社製「702C」、総繊度1670dtex、単糸繊度5.80dtex)を浸漬した後、ローラーで搾液した。次いで、得られた繊維を130℃で60秒間乾燥処理し、更に240℃で60秒間熱処理して巻き取ることで、親水化処理を行ったPET繊維を作製した。
水 :96.96質量部
メイカノートDM-3031 CONC : 22質量部
デナコールEX-614B : 7質量部
親水化処理剤にはブロックドイソシアネートとエポキシ樹脂を用いて調製した。なお、ブロックドイソシアネートとして、明成化学工業株式会社製の「メイカノートDM-3031 CONC」を、エポキシ樹脂として、ナガセケムテックス株式会社製の「デナコールEX-614B」を用いた。
実施例9、10、比較例3、4及び参考例2、3で得られた繊維コードについて、前記と同様の方法でゴム接着力及び初期引張抵抗度を評価した。結果を表3に示す。
Claims (13)
- 親水性繊維及び接着成分を含有する補強繊維であって、
該親水性繊維の表面の少なくとも一部に該接着成分を有し、
該接着成分が、共役ジエン系ゴムの一部に水素結合性官能基を有する変性共役ジエン系ゴムを含み、かつ、該変性共役ジエン系ゴム中の水素結合性官能基数が1分子当たりの平均で2~150個である、補強繊維。 - 前記親水性繊維が、ポリビニルアルコール系繊維、再生セルロース系繊維、及び疎水性繊維の表面を親水化処理した繊維から選ばれる1種以上である、請求項1に記載の補強繊維。
- 前記疎水性繊維がポリエステル系繊維である、請求項2に記載の補強繊維。
- 前記補強繊維が、単糸繊度が0.1dtex以上30dtex以下のマルチフィラメントである、請求項1~3のいずれかに記載の補強繊維。
- 前記変性共役ジエン系ゴムの数平均分子量(Mn)が10,000超200,000以下である、請求項1~4のいずれかに記載の補強繊維。
- 前記変性共役ジエン系ゴムが、分子内にブタジエン及びイソプレンから選ばれる1種以上に由来する単量体単位を有する、請求項1~5のいずれかに記載の補強繊維。
- 前記水素結合性官能基が、ヒドロキシ基;アルデヒド基及びそのアセタール化体;カルボキシル基、その塩、そのエステル化体、及びその酸無水物;並びにシラノール基及びそのエステル化体から選ばれる1種以上である、請求項1~6のいずれかに記載の補強繊維。
- 前記接着成分の付着量が、前記補強繊維に対して、0.1質量%以上10質量%以下である、請求項1~7のいずれかに記載の補強繊維。
- 請求項1~8のいずれかに記載の補強繊維の製造方法であって、下記工程I-1及び工程I-2を含む、補強繊維の製造方法。
工程I-1:前記接着成分を親水性繊維の表面に付着させる工程
工程I-2:工程I-1で得られた前記接着成分が付着した親水性繊維を200℃以下で熱処理する工程 - 請求項1~8のいずれかに記載の補強繊維を少なくとも一部に含む、織物又は編物。
- 請求項1~8のいずれかに記載の補強繊維を用いた、成形体。
- 更にゴム成分を用いた、請求項11に記載の成形体。
- 前記成形体がタイヤ、ベルト又はホースである、請求項12に記載の成形体。
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Also Published As
Publication number | Publication date |
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KR102704519B1 (ko) | 2024-09-06 |
US20210222036A1 (en) | 2021-07-22 |
JPWO2019230700A1 (ja) | 2021-06-24 |
CA3101958A1 (en) | 2019-12-05 |
TW202012137A (zh) | 2020-04-01 |
JP7314128B2 (ja) | 2023-07-25 |
KR20210014107A (ko) | 2021-02-08 |
EP3805451A1 (en) | 2021-04-14 |
CN112204192A (zh) | 2021-01-08 |
EP3805451A4 (en) | 2022-02-23 |
JP2023083374A (ja) | 2023-06-15 |
CN112204192B (zh) | 2023-12-01 |
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